Georges Hadziioannou, Paul F. van Hutten (Eds.) Semiconducting Polymers Chemistry, Physics and Engineeringae Bid Rp Cyn ai Ce prema es esate Bekebe ‘Deut of Poa Chi nd Mais See Cet Uieniy of Coogee Neco tA? AG Gangs ey of gs Ce Ne. apt fo ‘Acs ed hi en nite tee eh Libary ‘De Dag el C-bit fsa ae eae tt De Doce Bok oa {© VOLE VCH Vg int, 2-049 Wena Fel Ri of Cra), 2099 ‘Al ig rece cig ta of aan a gg). Nop of i ay (not sy tn apo ese” wt (oops KeV Fonte Gal, D420 Won Ping tte Gt. tam ‘shat 1 Sater Gast @ Co KG, DOTS Gs en ie Fed Rep of Cry Preface When siting shout a subject from a rapidly evolving seszarch aca, one is tempt into deskng with the Lae ul, ho that nll ne This da [peos, however for sack ndings amy a have a sng vale. "They may ao Fe vuicierly unambiguous, evgcarg, ox novel vo deserve thei ple in 8 r= ference work We lave nv sa colleagues 1 write shout tho ello expec, and pa own ony ts things that thy ae wally consfonble with, atl comin! of Fomunsicly. we found many willing o comsbute its velo With help, we Inve treo ble ellct much of ctw one st es boon gator in's desade of macrch on senicondting polymers. I Tocognied, of couse that esearch ints ek could bud om wht ad at ese about conducting "We like wo thank tone who cllsorate inthis book projec. This includes all sua, a2 wll ay ae people a Wiky VCH bo eller wn the oppertanity and ‘made bose veal. Georges Haieanno Pol van Hate Groningen, Septenber 19)Foreword The science and technology of conducting polymers are inherently interdisciplin- ary; they fall at the intersection of three established disciplines: chemistry, physics and engineering; hence the name for this volume. These macromolecular materials are synthesized by the methods of organic chemistry. Their electronic structure and clectronic properties fall within the domain of condensed matter physics, Effi- cient processing of conjugated polymer materials into useful forms and the fabri- cation of electronic and opto-electronic devices require input from engineering; i.e. materials science (more specifically, polymer science) and device physic With the emergence of semiconducting and metallic polymers us an interdisct plinary field, « host of new concepts have evolved which are of broad and fun mental importance. The field originated in the 1970s with an initial focus on n- type and p-type doping of conjugated polymers. Reversible doping of semicon- ducting polymers was the early highlight with associated electrical conductivity values that span the full range from insulator to metal. The unique electrochemis- try of conducting polymers was subsequently discovered and remains as an active area of science and technology. The opportunity to synthesize new conjugated polymers with improved proper= tics began to-attract the attention of a larger number of synthetic chemists in the 1980s. Equally important was the subsequent development of stable, processible * metallic polymers. As a result of these efforts, we now have a class of materials which exhibit a unique combination of properties: the electronic and optical prop- erties of metals and semiconductors in combination with the processing advan- tages and mechanical properties of polymers. Because of the progress toward higher putity, processible semiconducting poly- mers, these materials are now available for use in “plastic electronic” devices. In this context, the discovery (at Cambridge University) of electroluminescence from semiconducting, conjugaicd polymers, was of particular importance. More gener ally, however, plastic electronics devices include diodes, photodiodes, photovol- taic cells, sensors, light-emitting diodes, lasers, field effect transistors and all-poly- mer integrated circuits — and the growing. Thus, the emergence of electron- ic and opto-clectronic devices fabricated from semiconducting polymers has becn a principal focus of the 1990s. Despite the scientific progress and the demonstration of novel device concepts, there was considerable skepticism that semiconducting polymers would ever reach the levels of purity required for long-tifetime commercial devices. In the context of the last SO years of scmiconductor physics, conjugated polymers were oftenVil Foreword eld “ty” nd pooty charmed ein, Teco the rt de Imenstation of bigh-bighiess polymer emisive displys with operaing Hits ‘0 10UK-20000 hours was 8 paricusy porn scp 1 now ca tht Senicoadvting polymer canbe inl w fou comer picts at est neil speteatcns. ofthe rea pat hea, i dae SE A efitng of noaaton Fae echoes ee eee ete le spin the scence an technology have moved ino new crecins. Specie esa ps uf cee aiveanes (whl dae 1990) Of oped norte tale We lowing: Metallic polymers which are sable, scluble and procesibe, and therefore suit- eee el The scence and tehnclogy of high-fiincy light emission from polymer Igicerating doar snd polymer ig-enatingckevochemeal calls Ulrafast phooinduced clon uansfer in semiconducting polymers mised ‘with cortlled ans of aexptr; tis penton ha oped the wy 10 I ee eth eerste ‘en plas sla ets «Soman polyresas matenals tor sou ste ser. “Ts toch, “Seuneoncing Felyers ~ Clann, Pigscs at) Ergin”, td by Gconees Hadricisnou end Paul van Halen of the University of Gro: ‘ingen (The Necns) summarizes progress ia ares of carent scuviy Wit (he fatl The veto chopor all consid by iading scarcter, provide ‘mary sd eview ofthe Rei that wil be uel and portant Yo anyone sek Ing 2 sorg bacsground in te bale Hcsplnry science a an Upc “aphot™ ofthe curent Salus of researc, Exnhasis i onthe Bie physics sud cchmisty of conugued polymers as elctonic and ope-cccuonie matrals ad ‘nthe performance (tats, Opportunies and Unites) ofthe sloctoni and “eleonie devices tat ze respite forthe on gouy, evokaion it “Fk ‘Alen J, Heeger Tofestor of Physica & Tofeaoe of Mates Tnstite for Polymers and Organic Solids University of Califor, Sana Batra UNIAX Corporation Santa Busta, CA Contents 1 Palyaryene vinylenes~ Synthesis ana Appteations Jn Semiconductr Devices "1 Michael Mt Murray and Aude B. Holes LE taweducion 1 Tan) Wren eset arene all nesenter 2) 121 The Basle Polymer LED Device Achiecture 122, Subsimed Folyiphenytene vinyls 0 1221 Poytantylenevinyeae)s 10 123° SrepGrowth Routes 0 FPV Desvaives 10 13” Refining the Properties of PPV ~ Mattliyer Devices 13 13.4 utuiajer Devices: The Incorporate ‘of Chase-Tarspoting Laver 132, Elesten Deficient Polymer Leminewsrt Taaspon Layers 16 132.1 Other Eltron Dalit PPV Davaives "19 1322 Flecton Deficient Aromatic Syiens 19 Vg Full Color Doptays~ the Sete for Blue Emiters 21 14.1 olsted Chromonhores —Towarls Blue Eniesion 21 142 Comb Polymer wih Chxaopores ot the Side-Chaia 22 1S) Ghia PPV — Petrized Enminton 23, 16 ——_dyibeny ene vieyenc)s— ‘Sule Cl of Low Bad Gap Mucils 24 161 Opanie Fett Fler Tease (FETS) 25 162 Synthesis 6 163 Alt Rowe 27 16 Ring Subsinued PTY Derivaives 27 165 ViayleneSubsituted PTV Detvaives — Tuning the Gap 30 17 Conclusions and Outlook 31 Acknowledgements 32 Reternces 3224 24 222 2B 2a 242 243 as 22 33 35 a a 44 442 483 4s 36 Contre Oligr- und Palyiphenylends 37 Utirch Scher and Klos Willen tewrcacion 37 Polymers 37 Oxidative Condensation of Benzene Derivatives 38 ‘Tanai Metal Matiated Couplings 39 ier Rouen 10 Poly(p phenjene 48 Obgoners 30 [Denane and Hyperranched Poyiphenylenes 35, petbrrchod Poy(phenylene) Desivaives, 35 Obo(phenylene)s Composed of Ontogeny Aranged Arms 56, Dendetic Polyipenylenele and Gat Pelyoromatie Hydrosurbore (Pali 57 Cosctsen 0 Releroces 61 Disorder and Solitons in Traus-Polyestylene 63 Jesper Koester and Mon Bostonoy ‘The Peierls lschility se Solitons 65 Disorder The Fucuaung Gap Medel 71 Pinder nde Kinks 76 Concluding Remaiks 32 ‘Achuuwledgenens £9 Referenes 8 Gas Phase to Sold State Evolution ofthe Electronic Zhigang Shui. and Jean-Luc Brides Ineroduction 87 ‘Theorical Mathodclogy £9 Warefincion Aaysn the Excited Stes in PPV Ofigemens 90 IneretainItericons ‘Absorption Propenics of Highly Syamecal Compleres 94 Photoluminescence Properties of Highly Synaral Complexes 99 ‘The Influence of the Nusrat Relative Ovations ‘Custer of Senitheny! Molecules 107 ‘Covetusions and Outlook 1 Acknowledgements Ut References 1 51 32 522 38 54 Sar 33 33a ssi S312 a2 5521 3322 5531 61 63 6ay 642 654 632 633 66 ben 662 ber 6622 uctronie Structure of Surfaces und Interfaces in Conjugated Polymers 115 cet Logdund nd Witham R. Saanees luudicion 115 Photoelectron Spectroscopy 116 XeRay Phovclcu Spectoacony 119 UnrvilerPhoweectr Specroncopy "120 Teal apester a? Maras 128 [Bleaonic Sucre of ram-Fotyactylene 123 Charge Storage Saks in Conjugated Paynes 125 Polyes Surfoces ard tertacen 128 Polyyertemienevinyere 138 lactic Fora Retwera Alig and PPV. 130 Inertace Formation Between Cac and PPV 132 Inno Formation Betwece Alumigu and Plyhiophene 135 ImtertaceFormusion Between Copper ani Palytopbene "137 Potanitan 139 Polyaniline os Indium TarOnide 140 Summa (4 Achaowledsenents 148, Reterenes 146 lectronie Structure and Energy Transfer ln Sold wSexthing! 129 Carlo Tabuni.Fabi Biscarin, and Michele Muccnt Inerodcion 149 Experimental 151 [Eeied Electronic Sates in lated T, 152 Sie Cryst Elosrnie Suosire 158 Darydor Siting 159 Heraber- Teller Vibwosie Coupling 160 Growth in High Viewumn 164 Thi-Fiim Morpnoteey 103 Scaling Behavice of Surface Roushness 16) Dasrdet EMet on Energy Taser "174 Single Crystal Fuorocence 174 ‘Thi-Fln Fuorescene 17 Morphioogy Dependent olrvaten 0! Fluerscence tial Eectrolummecence IL Momtology-Dependent Ear Taster 184 186xt 7 m n 71 722 23 Taa B 732 Ba Ta 742 is 734 16 4 rn 85 832 833 a7 85 Contes Spectrascopy of Fhotoexcitatons sn Conjugated Polymers 189 Paul A Lane. Sergey V. Fre and Zev V. Wardens Iauoduction 189 [Experimeatl Techniques 190 CW Photemodstation Spcroscopy 190 Opsicaly Detected Magnetic Resnance 193 “Tmnslem Phovomodulation Spectroscopy 196 ‘Now-Linear Optical Spectescoy, 193 Polyparephenylene vnylene) 202 ieee ar eereaeeaie ‘Tresien Phowoodulation 208 [extLinear Spearosopy (TVA and EA) 208 GW Phtomousion "211 Potyhophieac 214 “Transient Phowwnedulain 215 CW Plesinmaltton 220 Falkrese-Doped DOOPPV. 226 Transient Phecomodutaion 225 Sommiry 202 References 232 ‘Photophysics of Meth Substituted Poy(para-PhengleneType Ladder Polymers. 235 Guithtno Lanza Sandro De Sibestr. Gili Cer, Sahetore Staging, Bure Mol, Will Grape Gunther Lions Ulich Scherer Kl Ballo Introdction 725 ‘An Overviow of Previous Reits 236 pial Proper “237 Experimental | 239 CGarnenioal Purp Pate 239 Fok Anaited Panp-Probe 240 ‘The Primary Photoerctins ia m-LPPP 241 (Oneview of he Expect Results 242 [A Model for m-LPPP Eksroie Suuctse 243 High Excitation Density Seenaio 247 The Emicinn Process tn me PPP 248, Garge Photgenersion in m-LPPP 250 Guichen 256 Refacoces 257 10 rou 02 103, 105, Ha Te nau 22 nas Coens Xi Sola-state aspects of Conjugated Semiconductors 239 Wilhelm Graupner: Sean Tasch, an! Gumher Lesi Induction 259 ‘Materia 260 Fuetionaities in Devices 262 (Garin ConjgtedSemicondustors 264 Excite Stte Spectroscopy 268 Excited Ses "269 [Neutal Photoescitions 271 Charged Psoerciaons 274 [letroluninescene Devices and Meds 282 8 High Defect Concension "243 EL Devits fram Conjugated Peyers wih 2 Low Defect Concentration 285 lecuolumiosceace fan an locwochemieal Cll 286 Carer Injcuen ar Charge Trapt 287 ‘Thermal Bmision 288, ‘ekeinduced Incton 2 ‘Chery Recembitation sel Eiieney 295 ‘Highly Excied Conjugate Filmy 297 Goreiatere 300 ‘Acknowledgemeats 303 Neterenes 308 Lasing in Conjugated Polymers 308 ‘aud Jochen Fednane Inrodction 309 ‘Stimulation in Organic Motels 310 Gain Narowing in Conjgsted Polyner Thin Films 317 {Laing im Conga Foye 321 Gulook 325 ‘Acknowledgements 326 ‘ependn 327 ‘Aprende 328 References 328 Kallingen ses of Polymer Ligh-miting Diodes 333 1H Campbell nd D1 Sth Iesoducion 333 Thi Fs of Elcrluminescent Polymers 335, Blectonic Enngy Scie 336 Opucal ropes 336 Bketitst Tans Prope 38Come Devise Betnnie Stxsune 339 Jel Phoemission Measurements ‘of Schoky Energy Bares 340 Bail Potential fo Device Sirctuce 242 “TwoCarie Suuctutes 352 Muli-Layer Devices 355 Transport Layers 359 ‘we-Camer Mut-iayer Devices 301 Cencusion 3. Referees 363 ‘Charge Transport in Random Oryanie Semiconductors 365 Heine Bassler Induction 365 Charge Cane jection 367 Concepts 367 Space Chae Limited (SCL) Cuments 379 he Concept 379 Experimental Resuls 381 (Charge Cam Transport 384 Goncents 384 Transpor inthe Prseice of Exinic Traps 390 Game Camer taspor in Conjugated Polysies 9% Time igh Stats 398 Transient Absorption of Radical Cations 403, Sees of Charge-Carying Moietcs 406 ‘Acknowledgements 407 References 48 “tne Chemistry, Payies ana Engineering of Organi Light-Eniting Diodes 411 ok Campbell Set and George G. Malkaras Tnuradvction 410 Muri 413 Conjugate Polymers. 413 Small Molcales 416 Molscisly Doped Polymers and Polymer Blends 419 Salt Acer Layer Langa Dlg Layer, and Liquid Crystals 420 Elects and Inerface Medication 421 Conta XV ‘Anodes 421 Cade 422 lets Maxieation 423 “Transparent Ctbodes, 424 Device Stacie 424 Device Characteristics 428 Pigurs-or-atent 429 Bustin Ptenial “430 Barer Heights 432 Charge Transpo 433 Photchuminewcence 434 Device ysis 433 “The Elementary Process 436 Single-Layer Devices 438 aac Theory 38 Nomi! Simons 439 perineal Stade a) Muluiyer Devices 443 Bctochenteal Cale 443 Mictewvin 428 Degradation 485 ‘Applicaton of OLEDS ws Pa Panel Daspays 49 Display Engincering Units and Conversions 419 Pixels Pateing, and Drivers 450 Encapsulation 455 Outeok 436 ‘eknorlsgements 457 fom BT Phases of Onyanic Field Pet Transintrs 46% Giles Horowite Invoduction 4683 Basie Pipl 466 Jones 464 ‘Mesa Semiconductor (MS) Suncion 464 Fonration of tieJunction "dea ‘The Juneuon a Equa (Zo Biss) 465 Coron Voltage Chartrnie 66 ‘Nl lasular Semiconductor (MIS) Junction 467 ‘MotalaseltorSemicvaductor FET (MISFET) 472 Piacipl of Operation 472XML Cmte 142212 Curent-Vologe Charetrsie. 473 14232 Mata Semicondactor HET (MESFET) 475 14223. Thnfin Transistor (TFT) 476 122231 Atcumlaion Moe, Line Regine 477 142232 Depletion Mode 478 14223. Accumulation Mode, Sauration Regine 480 142234 Mebily Threehold 461 143. Charge Trarsyom in Oranic Matias 481 1431 Lovaied Venus Delocalzed Sits $81 1432 Heoring 483 14321 Hopping Rate 483 14322. Polaron 486 143221 Polaons in Conugsed Polymers 486 143222 tranpon Meehan of Paros 34 1433 Multiple Tapping and Release 486 1434 FikdDepesent Mobility 487 M44. Fubricaite Techniques 408 1441 Depesition ofthe Semiconductor 488 T4411 Elecwopolymesizion 489 Solution Processed Denostion 489 Vacuum Evaporation 89 Langmuir Blodget 90 AlLOrpanie Devices 490 Oligttionhencs, 492 (Other Smal ests 495 Pentsoone 456 slype Semicon 498 Polymers 499) Models 300 Temperture and Gate Bias Dependence S01 Trap-Lanted Tratspor SOL olan and Hoprang Madets 308 Curen-Vokage Chartres 507 Shor:-Chanoel Elects SOT Conelding Remarks 510 Release 311 5 Conjugated Polymer Based Pstic Solr Cells S15, ‘Chrno. be tnd Senor Sri 15.1 nection $1 12 Canpgate Polytes as Powexcted Doron 516 1821 Opucal Properties 518 152.11 Linear Optica! ropes 518 is212 15213 152 133 1534 i532 1333) 1534 isa 155 1551 156 1362 87 161 Tel eta ors 162) tea teats te2t2 teats 62134 162132 le2t34 1622. 1e224 Coments XVI Phctoindvced Absorption 521 ‘Quenching of the Inesyac Ceosing wo the Tight State 521 Photoinduced IRAV Studies 522 TuneRentved Finda Silos 524 Sensation of Photecsnuctvily 525, ‘Magnetic Properties 526 Lightincad Eleron Spin Rosonasce (LESR) 526 ore Conjogted Polymur Phtoelisie Devices 528, Denon 328 Base Tiarpon Properties 528 MealConngsied Polymer Contacts 31 Spectal Response S32 (Conjugated Polymer Bilayer Devices 536 ‘Cnjuited oijme yg Heterojunction Mhotodiedes 339 ‘Conjugated Polymer Bulk Heterojaction Diades 545 ‘Conjugate PolynicrCyy Bulk Heterojunction Photuiodes S45. ‘Cogypnted PolyinafCajogted Poytner Blk {junto Phatoiodss 549 ile, Large Area, Pate Sola Cols St Subity of Paste Sor Cells 553 ‘The Guest Host Appoach ui aad Staion 555 ‘Reknowieaeniens 336 References 337 ‘A Medel Ofigomer Approach fo Semiconducting Foymers 36 Poal ven Hatem amd Georges Hadioanno Iauodsion S61 Background S61 “The Copolymer Approick to Cento Light Enision in Poymer 562 igs as Meds! Compounds tor Sicure-Prpeny Studs 363 ‘Syiubais a Seluion Properties of OPV S64 Syruboss 564) General Statery 565 Syathess of Model Compounds 566 “Thre-inye OVPs 366 Syathess of wOPVS "567 Syuthous ef oct OPNS and Oost OPS S66 Syatheis of Cyano Substituted OPV3s and OPVSs 568 (puteal Propetes im Seualon 362 Compson of Coplyiery nd Relat Oligomrs 569 “Three Ring Chromnyiins 56)XVI Contes 162212 1a 46223 163) Wea 16312 163122 163193 tessa w6a1a3 Tessa fes135 les136 testa 133 Tossa 16332 reagan 163399 163323 es3a0 16333) 16333 16a teas 6a 16a 16423, 1ea3 16432 Index 15 Fe Ring Chromophoes 572 Suton Ect io OFVS8 573 ‘Aout the Geom of te Exc State 576 OPVs ine Concent Sie 577 Sint Costs Ietmdhcton 577 Coat Stuctures of Five Ring OPV. 579 OctOPVSCN 580 OoecOPVSCN” El Cet See Tice Bing OPV S27 Ooaorv3 582 Oneorvs 382 Ove OPVSCN 583 OsecORVSCH” 385 OucORV3 5b OS-OPVS-N™ 384 Optical Popes of Single Crystals 585 Theol repre: Lig. Crysolen Phos 58S Thin Fle "588 Irian "388 ‘Thi-Flm Sinture 589 GcccOPvS 519, Cpanel tteeenyy £60 X'Ray Dian (XRD) 589 ‘ome Farce Micnscny (AFM) 590 fcrorvsen 392 OrccorvscN” $92 Gecconvs 32 ial Poperics 594 Seka orvs 393 Geet 97 Light Enision Applications of OPVs 598 fatocton 398 Leh Eating Diodes 599 SingleLayer Devices 599 Talos oe Mertatigy x Device Vacate: 672 DasbleLiyer Devices 603 Stimuli Enision 8 Single Crystals (Ot Vidwom Bpored Flas 605 ‘Senay and Owe" 608 Acknowledges 610 Referees 10 List of Contributors H, Bike Irate or Pnysiat, Nukes snd Mcromecuba Cheisty Philipp Univesity of Marburg 5082 Maus Germany D. Bojan Service de Cisse fds Manan Nouveau (Centre de Recherche en Flstenique ft Phooriqae Moiseulires Univers Se Mons tase e700 ons Belg Bsa a Tstto d Spetucacopa Molecotse Conve Novena dele Rees Vie Gobet, 01 140129 Boke Aly Ghrisian Doppler Laboratory Physical Choisy bene Kepler University Line ‘Abeobergsnate © ‘a0 Lire isin Jo se Sertce de Chic es Noten Nowveana (Cane de Recherche en Bectonique Pee Moles Universié de Mons Hainaut Place a Pac, 20 18-7000 Mons Belge LH, Catt ‘Lo Alanis National Laboratory Mai Stop D&29 NM Br3es Usa. oom Tito Nazionale perf Fisica sets Macs Polen 0 ino Pizza Leonard Vie, 32 1.20133 Milano tay 4, Com ses Matrix Nowweaux ‘Gane de Recherche en Eksrnique Phosnaqse Malcaees Univer de Mon tian Mae Wu Fae, 20 7000 Mons 8XX Late Comrbaers Istituto Nasional per ka dela Mates Dipatimee di Fisica Politecnico di Milano Placen Leonardo dla Vick, 32 1.20133 Milano aly A. dos Santos ‘Serie de Chania (es Matiaux Nouveanx ‘Cente de Recherche en Electronique 1 Photonique Moles Université de Mons Hast Place dy Pare, 20, 18-7000 Mons Belgium 4. Felden ett fr Phone und Optclektronik Selaon Physik und Corer fer NanoSecnce [adwig Maxaman Universitat ‘Analensae St D-E0799 Munchen Gemany SV Fiotow ll Latorataries Licent Tecolegics (OO Mountain Ave uray Hl Non USA 1, Graupner ‘ings Tee Deparnent of Physics ‘Blacksburg Va2406-0635 Usa ©. Hadioannos Deparinent of Polymer Chemistry and Materials Science Centre University of Groningen Nignborgh 4 NUS247 AG Groningen ‘The Nederlands ‘A, Haugenecr Cenex fir Photon tind Opectltrome Sektion Physik und Center for NamScence ‘ini’ Manin Universit Minchin ‘Aralomarie Sa 80799 Munchen Gera A.B. Holnes Unies Chiat abertay Deparment of Chemisry Lele Road CCanteige CB2 1EW ‘Unite Rangdoon G. Horowitz [borate des Moriaun Mokeaaies CNRS, ER 241 hnger Cant fr Prowaik ‘ud Optoetekronik Seltion Physik und Conte for NaroSctence Lig Maxima Unvenitt ‘Amaliensnte 54 D's0799 Munchen Genny Taste for Tacortcal Physics find Matias Science Core Universiy of Groningen Nijeborgh 4 EDIT AG Groningen ‘The Naberbnds PA Line Depart of Fysins and Astronomy Univesy of Sheek ‘Sheffield $3 78H Unied Kingom G. Lanant tate Neonat per a Fisker dels Mater Dipti dt Fics Potter Milano Paces Leonard Vie, 32 120133 Mito aly Lesing Insti for Festkerperpysk “Teche Universi Graz Patergine 16 A-6010 Gee ‘usta U.Lemmer [test fir Poco tnd Optocleltonik Selticn Physik CMs Munchen ‘maliensiae 54 0799 Minchen Gennany 2M. Logatund (Cabortry Manager IMCHOF Braden 34 ‘$221 Ronkeping Sweden us of Certaues XD 6.6. Malars Deparcat of Materials saad Engioccing Corll University S027 Bard Hall iMhaca NY 188531501 USA 1M, Mosovey Teste for Thoetical Physics tnd Materials Science Centre Unisenity of Groningen ‘Nijeaborgh 4 NUTT AG Choninge ‘The Nesands| 1M. Muceiai Iaiata di Spettoscopia Moleolxe CConsigito Noche delle Ricerche Via PGoten, 101 140129 Boog tly K, Men Max Plonck-tostiut far Polyrerionchng ‘Ackermann 10 55128 Maine Gamay MM. Muray Fi Lily S.A, Durden Kral Co. Cork Irland QSECKR Poltecice di Milne Piazza Leonardo dt Vin, 32 120138 Milne IulyXI List of Contos WER. Salaeck Deere of Physics. IFM. iki Univerity Soal'aa Linking Swoden NS. Sai (Cristian Doppler Labertory for Pati Saar Cole Fiysical Chemisty Jlnnes Keper Univers Linz U.Stet Mav Pianeta fir Polymatoschung hetermmeanieg. I Ds5128 Mainz Gary 4, Seat IBM Research Division ‘Almaden Research Center (20 tery Rem Sen Jos CA 95120-6009 Service de Chimie (Centr de Recherche en Electronique ft Phowrigue Modulates Univer de Mone Haina Place du Pare, 20, ‘B70 Mons Betoun DAL. Sith Electonics Reseach Group {Lor Alte Rational Latiory Mal Siop D129 NM ASHS US 5, stgia Teta Nzonale perl Fisica (ls Materia Dipertieet oh Ft Politenico di Milano Piazza Leonaro 63 Vite, 32 1.20133 Milano Italy Taian Tatu di Spetroscopia Molecomre (Cemsigho Naionale delle Ricerche Via P.Gobat, 101 140129 Bologna aly Inst fr Feskonperpiysk “Textsetae Universitit Gra Patras 16 ASOLO Grae et yan Hen Deartent of Polvner Cheisry and Marval Science Cente Uniseraty of Oroningss Nienborgh NUSTAT AG Groninges ‘The Neha Department of Physics University of Ua ‘Sat take Cy urasilz Usa List of Abbreviations AEM, 20M DAD bearer UEH-PPV ESR re ‘Atom Force Microscopy couto-gpe mito mpi spontancows exision bis dipbeaylaninestyryl-2.5-dimetbonybenzene ply bing etyhony lo) pare-phonyenevinylene) Pub but 3. stytexl)-L phenylene vy) oncom bal ‘Soup leon oscil ‘conducting polymer hae piawgecation hae tur excitons CCoatinucus Wave ‘Sphenaniacatyryihonrene “depo ais par tlyamine (dened Brg reece ‘atibuted foebock ‘hers subsied 6T feb Sey per phanslnevinyene) oping indeed absorption aly sahocylory-paru-phesyene vinyens) Santen of tee enaiy-oF tes Gers a ence sas puly( 4 pnylene-12-diphenoxypnenylvinyene) Biter setanng commer Aileen raswsion ‘eporetlyl parr saisyamine ‘eral color eonvenion ‘lestron difiacton egy diibtion cue Electoumiescence uum Specttoncopy for Chemical Applicion fect pen resonance Felden wasXXIV Lis of Abreiaions PN Fro Gp Gre HOMO ar av, tec sore INDO re Isc. m0 ry tcp Lec LED Usk pe Luo MEI-DSB MEH-PPV MeLPrP MIM anne Mis MISRET LPP MNDO. Mosrer Ms MSA NTCDA ODMR oGm, oma’ comp ivcwating Gap Mowe Fowler Northam ‘cine doped tin dioxide emirate pair Cet Permeation Chromatography hishest occupied molecular otal Heraberg Teer igh vacua inten color conversion ulated gate FET Imrmedite Neglect of Differ Overlap incidemt photos to converted elesron Iatard Sve vba is Interystem crsang indium onde LangmuieBlodeen Tigi erat spy Iightemnting elecrcchenical cell ligh-emiing die Lighciinduced Elecron Sin Resonance Iaklered polyare pheylere) west uneccupied molecu obi Dvsthny-5 (-eytherylony)-14-is4-tyyayrytenzene Poly(-methory-5-C-ethylhexyoxy)l 4phenylene vinyine imetiylautstinted polyre-phenylene>ype ler payor 2 netalinwlitorineal micromoldng in capil ‘etl nslatorsemiconbctor ‘etal lator semiconductor FET ‘ety subsituted poly(oarehenylene) ype lier polymer ‘Mediied Neglect of Distosc Overlap ‘meul-semiconducior {es(e-methonyatiiens)amine ‘talienicondicerimca ‘rulipl uapping snd ermal ease ‘ophthlere wacarboxyic danhykide ‘opteally decid raugneic esoaance ‘tyne Fela warsstor ‘neta gas model igen geen ka ‘ptcal which analyze ‘organic molaclar beam deposition PLOY PrSVE RS SCLC SE SF sippy TAA Ls of Aresiions XX ‘gocprenyienevinylene) polyexythophene) polyG-ocyihiopbene) peed PA detected gcc resonance polyaromatic hycrocaon polaniine Pirotbleahing 2G biphenyl 5 Cerzbuylpheny}} 13 onadiacae Putaleeyanine photsde Peon digital asian pobiseyiony-eiy) Poby.4-thylenedioythiophene)poly(syrenesulfonate) paletiyiendioythiopene) olyh(4-(1"4" 7 aenaocty-shenyDiiopbene) potelecroa specwencopy Poste Freel parcbexapery Polonted atserpon Botolumiescencequsntum ytd PLedeteced mpi resonance pPhotomadalton posronapy Polymetiyincicryte {opolymer coming. phenyene, vnylene aed non-conj ated eticoe wits polydwne penylere) Pobphenyiphenlesevinylene) Febthionbne Foly(2.5-venpinevnyene) polvinylarbazale Richanbon-Schahy te itn basi Sinitel enon Sapeflnacence Poly(dietylene par phenylenevinylene 25-040 Spur pylon anton pr phen) ‘aming unmcling macnn inpaceausylanineTeng Lif Areas tereyunoqunodinethane ‘eaiadinethytanenochslene lranevene elctre modes ttansmision electron microscopy (Gini ace transverse magnetic max tie of Tight {wo-thatonabsertion tiparcecylanine sretigh vacuums UnravioletPhowelecwon Spectrscopy (UPS) avioet Pee ce xy Difacion 1 Poly(arylene vinylene)s — Synthesis and Applications in Semiconductor Devices Michael M. Murray and Andrew B. Holmes 1.1 Introduction Polymers hive wuditonaly been considered insuling mates by chemist and physicists alike Indeed 3 conventional aplication of plymer isthe sae lion of meus condiciom The scenipnea covery of highly conde polyacetylene, however, marked the bith of anew field (The sty of this few elas of compounds oes teed "olecuar clerk” and the sea hin rove 10 be highly incedscotinary in mature. Chemis. physicists and theorist Ske ae continually explong cw mules and. devising novel secelopes Ey studies foeucd on improving the conductivity of organic ply pos oping, bu i has been gency scepied tha most real deviees te ly 10 ex ‘lI the munnsesemiconductive properties OF tese mates Plyaylenevinyeues form an ingertant class of conducting polymers. Two representative examples of is lass of materials wil be discussed in Some detail Innes Thaw ae puly{ 4 phoneme ssylene) (PPV) f,poy(]4 higne iy lene) (PTV) 2 and their derivatives. The polymers are cancptualy similar, PTV say be considered 3 Herve aualog of PP, bu has cnsierbly Toe Ind gp and exhibits higher conductivities in both is deed and usenet, ‘The semcondysirg progertn of PPV have een shown 10 be sell ithe manufacture of chewoluminecent devices, whecis the poem uty of PTV Tas yet to be fully exploited. Tis accous wil provide a review of syetc pps to aryene viylene Genvlives snd wil ive deals sn how the sino ‘rs ofthe mate late to ir perfertsner i fal deviers Oy, ry,2 1 Pees vile — See and Applications in Seniconactor Devices 1.2. Poly(1,4-phenylene vinylene) and its Derivatives ‘Bectcuminscence was fet demonstrated for conjugated polyincrs(eg. PPV 1) at Cambridge in 190 (2), PPV is he cheapest and simplest pely(anene vnytee), ‘ommening of alereating benzene and vinvene unit. The material high uot ‘ead s right yellow in coos crassion maxina ae inthe yellow-green re {Ghote voile spcnan and two etn emission peaks ar radi inti: 551 am (225eV) anda 520 nn G4 eV), The synthesis of PPV was first described in he Ils but the inal material obained was soluble, infil, and fc 10 ‘wocss. The high crystallinity of conjugated polymers i believed to arse from Seng interchain x stacking cations. Soluton processing Isa highly desir. “dic anaeisic a allows the satel to be cowed cheaply and incorporated into EL devices: PPV forme excellent wansparet fms when ct fom sluvon orupon spncoutng, Syeticte oul have bora develope allow ial eunver Sion 10 PPV fiom varity of sole recurs. Weslng and Zinmexman ino ‘ced (3, 4] he slfonium recurso cou i PPV. The wou has subsequently been ‘Spat and eed by oder enearch groupe [5-7] hae an een el 0 pea ff inthe syetsis of several etvatives of PPV. "he chemetry tehind the syriess of parm PPV is rltively stsightixward sad is ulined in Schene 1-2 A sulfide sich as tsahydroduophene raced Scheme 12 Syrtsis of PPV 1 2) ialyemeptere, COM, 65°C: t) NAOH, MeoHY Fibre BahGnl Neon, 0%, cj rtaromion hays Ia) MEOH. 50° 120°C, HOA), 22h) 205900. voc, Te 12 Font plergtene sine ns Denaves 3 with a-ichlorop-ylene 3 1 yekd a bis-sulfnivm sh 4. Dimethyl sulfide has iso been used bur metyfsltenim groups Were Tound to undergo ltrs Side-reactions in subsequent sips [3]. Dsslving the monomer 4 in methanol aad trestment wil agccus sigan hydroxide at O-5'C results in polymerization vit the quinomethidemrmeriate S- Considerable reser ellet Ha dteraiped that the optimal rely are achiev if slighty less shan one equivalent of base pot Imo of muon pac Easias tane pronate chiinaion to highly colonel Conjugated mei whores insuieent base towers polymer yk. The ection {S'best conducted under inet auosphere and is trminaed by the atin od (hyo seid. Low rickcuibr weight impuriies and sts are cemaved by ily wo alfod almost cokes soluions of precunr polymer 6. The nok far weigh of the recur ply my not be easly determined by gl-permes tion chomtography (GPC) txcaise i isoluble in conventional GPC solvents Such ay eoofor, THF, and tlucye The mail iay, however, be elle a Icha tere upon te alla gonp place by a methoxy subsea ‘The resultant neu polyiet 7 i soluble in comin Orc selves and is thunder averigs mola! man My hs bes dteriined to Be tas 100000 g/t “The ricchansin of this poyerization has teen extensively investigate. The high molccalar weights and tap ue Ot polymerization pot to 3 radcal mecha fw ia a suinonichie interme. hs been shown tha radia Wapping “igen such ss molecular oxygen lower the palymer’s molecular weight [4,8 Frter studies by Vanderaede lend suppot to this hypeesis 9], and recat ‘work pear to hve ruled out annie propagation. “Tun inn Of te poner precursor © may be couverted tao fully conjugal PPV’ by heats within the tergertue range 180-300'C for 12 hous unde ‘actin [2, 6) These condons favor the renal of the reation’s by-products {ralyotitophene se hydrogen chloride. There ae pets that dhe psec i fonyeen during the convesion his a deleterious effect on the luminescence quan fm efficiency ofthe fina im. tt belived that oxygen pronase Fomor fof earbonyl groups which qucnch lininecence [10-12]. "The conversion temper fre may be reduced to 100°C by using the bromide rer than the chlonde sib ttpmeurer polymer 6 allowing the prepatian of IED en fesble payer fot Sitntrats (ee, 1TO-coated PED) Langinui-Blodget techniques have also beet {hed to deposi PPV (13). 1 hs recenly bees detonated that wel liged dt fins ad fibers of PPV may be formed by pre-ordering the precunor polymer ¢ ina lotopiciguidcrytline phase before ternal conversion. Such s'nanocom poste has potent applications foe pore eaaon (18) “There have Been a numb of eter routes to PPV reported in the fier, bu sme reuing device hctines sa elicecy vary consieably. The Wein rst tas Been moificd by employing a sli group instead ofa slfonum gro [15-17] "The polymervation Fs believed 1 prose by the same quinomedid ia termestte and fos PPV upon thermal conversion. The route complementary to the Wessling mbox the pracusor polymer is soluble in organic solvents {Gavin et of [18] reported hata nana procs rote affenin higher devi. fences thin the sindard tou. PPV nay also be syihesized by chemncs Vapor deposition of diaogensedpxyenes 3 and 9 [19] oF oF she chk41 Petferinevinlnee—Sybess nl Aplcations be Sanactr Danes ~~ So ie at wet Som $- 4H) wan woe + Or, Schame 18, Atemathe sys rales to PPV 1:3) S20-700%, 061 mbar t) £80, tare) bot cun tome en Go", ag) oC va) HAN, 9, ‘clone 6 1201. In eich case the iene elo preeunoe polymer 10 is ‘ermally convened to PPV at 200°C under vacuum (Scheme 13) These meth (068 ied FP with ow (DIAZ) device etticines (1, 2 ‘Avsiylene is posphorium salt I gave fils of PPV 1 pon electopeymer ination. The absertion and emission sects of the esulkast mesial were blue ‘lied wih respect wo PPV produced by elle routes, suggesting that the eleceo- polymerized materi as a shorer effetive conjugation length, posibly because ‘Of inconplets emanation of phesponim groups [22 ‘A potential drawback ofall he routes discus thas for i tha ther i ite ‘conuol over polydispersity and molecular weight of the result olymer. Ring= ‘opening metesispolymnerieation (ROMP) i living polymerteton meth Bd, in Weory, affouls materials with low polyispersites sed prediable rok fee weights. This metnoaoiogy has Been applied to the synens of poyactyere by Feast [23] and has recy been exploicd in the sythess of PPV. Bicycle ‘monorier 12 [24] and eyclophaue 13 [25 affod well-defined precursor pulynes ‘which my be converted imo PPV by thermal elimination an dened Schee -4 12.1 The Basie Polymer LED Device Architecture “Tae simple polymeraied EL devon oni of singh layer of comicent ing uorescot polymer, eg, PPV, sandwiched bowen two elses, one of ‘which has to te tansparen (Fig, 1-1). Whet 4 vollge or bis fs applied to he ‘moter, charged ares (electrons and holes) ae inte ito the ctsye Ler fl these carers are mile unde the inven ofthe high (10° Vent) la 12 Pot pheslnevslene andi Devas a bs ‘oF AP On tO, ‘Sename 1-4. ROU oes PPV 1:2 Wx NACHE PHC: 9 BAN {HEX 80" 08 a0 Fare 1 Stemi vag a pee eran vce. A pa! ne Kel apna a fn arse egy nea pn FV ‘Sm hen ple ine ce Wie fed. Some of thee carers may recombine within the enissive layer yi Ing etched lecron-tee parm ned ekiions, These carom tay be proce” ineiher the singlet or pit sates and may radiatively decay to the grou ste by phosphorescence (PL) oF fuorscene (FL) pathways (Fig. 2) A importa Figure of mei for decoluminescent materials is the aunber of poten ete per elcevon iced and this tenned the iernal quantum eflcieney. is ee Teton, du the attical suaninuen ncenl econ for an EL. device 25% 2 only ose quaner ofthe excitons ae produced in the singlet site. In peat, this maxinuat vale is dimilshed further because rot ll of he igh nerd6 1 aban viol — Sythe nl Applications in Semconductr Devices or eae ate ou oS SS AS gue 12.2) ati + epee ce et HOMO LUMO. ta ‘phctcaiopet pte ere eyes chal upg an a he a en LN ey gap Sl oe dw oe laws a ponte won fg Schl fate ec pp nay rac yal oa wa et of ngs ke SRS See ee ee eee rckcn oma cme tect Te ang ans spat tye ch aes wr he tera prict ee eh whens sin cad ot sabes core or ante cb ‘ond cpl nc sd ph su ral tc nope gh visible tothe viewer. Some ofthe photons emit are relected by the polymer Uf sal he external efficiency. derefore. fa fctorof 2s? smaller than the in tema efficiency, where wis he relative index ofthe polymer ypically 1=14), “Typmal etc quantum eines fortis els of rites 0.1 2% (26), 122 Substituted Poly(phenylene vinylene)s ‘Conjugated polymers in genera have a propensity 1 aggregate or Stack 36 3 eon Sequence oftheir extensive m delocalization, Ths is a nitation of PPV ise as ies then procesing during device faction. LEDs fabricated fom PPV ‘Sven tt at soul in he conjugated form were ft epee by Obici ‘rad at Sutimoto (27) and by Heeger and Braun at Santa Barbas (28, 29). The Sb of the materals rests rom the presence of Yong aly chains which af Fond ore sonfermatinal maby othe polymer chifs. Asa consequence. the nates cad to have lower las ans trnperatures than PPV asl. Pure fore, the sullen grecuser polyner 6 is soluble in rahanolic solvents Inieress alos all sluble PPV derivatives are prcesible in solvers that Go not Chine swelling of PPV or ts sullonim precusee &. Mulliayer OF sndwich type 12 Pobt¢peeevnyen) and its Deratves 7 stnsctures comprising of dierent polymers (eg, PPV and subsuited FY) may be ficted, en hese exploit ts eferece in solubilities (30,31 Poly(2Sialkoxy-Lphenylene)vinyleneh. wit) Tong. solbizing alkoxy ‘tains dislve in conventional omanic toler much a chloroform, toluene, oF tetrahydrofuran (27, 28, 32-36). Thee emision and absorption spect ae re ited relative o PPV shel, and the poymers” uorescence and lecTOunes ‘ence quam yields ate greater than patent PPV. This Benet may be a eorse- ‘quence ofthe long alkyl chains solatng the polymes chains fom each ether. "Te salvia precursor coat ay ao be applied to sony sutinasd PPVin but a dshydatulogenaion condensation polyrenzaion route, pionecred by Gite, favored [37]. The polymerization again proceeds via a Gulrometnce i textes, fa the sje of the conjugated fer vequies only two SDS Sn peat often inproved yi. The sys of the meh tied ely iieony-3-C-aliyieaylony- I phenykne vinylenel, MEH-PPY 15 culined in Scheme 1-5 [33,35] The sluilay of MEH-PPV is believed w be exhnced pees tis eae P oy, Seneme 1.5 Proparnon ol MENPPV 16: a) Zetia erie, KOK, OH, ee 16 ‘je, ore Nt eonare, 20°C, Yoh ahs 4c) Ko TH, 20°C, 2th 4-Methoxypicaol is lkyue and then etlromehylle to yield the burr ‘weit denvatve 14 (8. 32-35] Polymerization and elimination fully eon {tal matral is promod by dhe adiion of 4 1Ofold excess of a base sich 3 Fonsi rerebutonde in crahyurolurar. The coneentton of bac and meno fer must be carly con Wo prevent e1os linking and gelation. The real tat MLILPYY m Ong red-orange in olor ine jer elcyolumninscence devise (ITOMEN-PPVICS) achieves an elfiiency of LO% [28 38, 39). The ‘quanti elciency may be improved outold by the incorporation of a hin Tote blocking yer of paly(aty! methacryaie) deported by angi Blodast techniques and by wsingaluninur 3s cxtode Other polyZ-aakoxy-1-pheaylene vinyls have been prep in si ‘ar fasion [34.35.40 411 Almatvely, soluble «halo recutor poet 17 ‘gy be buted by using lve than one equnvatent of base Scene 1-6) Tis tay thos te convened so flly conjugated mera 16 by Wenral wate “Tis fal precuner ouie may be prefered af the fully conugsted mtr his Tumi soli pcp conversion Is Cesc8 1 Poesene vinleney— Sati and Aplications a Senin Devices Scheme 1-4, Te Halogecusor re 0 subted PPVE: 2) NBS, CO, hb) KO Sha veo 20°C, acum, th op ~ 28 < tosan” Some, Bier OPM emtame mw Hoce-etue Late 1.2 Pobtt¢besene vise) and tx Dervatnes 9 Cont of gelation and polydsperaty as reccaly Been improved by We we ‘of a henryic baie 22 terminstor (Scheme 17) {42}. ‘The ale serves a a fon polymere acidic editive, and high molecular weight PPV derivatives 8 Wah sctedvey small pelygpanios con te atsnad. A hens rion live 284, DPGPPY, shows 3 remarkably high photoluminescence quantum ef tency of 59 tn the solid sae Hs emtsion mani) (490 nm) isin dhe We frcen region of the apecnan. The synthetic route i versatile and utilises the [Diels-Alder ration at a novel way of appending alkyl groups ono the benzene n "The effets ofthe lengh and degree of branching of the alkoxy se chain on EL efficieney have been examined by a numberof researth groups (Scheme 1-8) {27}. Ettwnncies pe though a maxima wih aceasing sie of side chain be- ere flling oll fot very large sutntauens such as chekstanony, eg 26 (40, 4). Tey te envi di sans lage subsite din te coicorseting ature ofthe materia by delcieriowswiting the polyre backbone, and also by incresing the insulating charster of he fin, The mnoduction of serially ‘Seoanding st grup uo DMOS-PPV 25 widens the HOMO-LUMO sap sd freon light i emed [44-37], External EL fences of 2.19 hive best Fepored by Pips using 8 oxy subsituted PPV desvaive 24 (48) amd an Setome 1 ays of soliton sisted HV donates101 Pabanione vines Syme at Appactons ts Somer Beves ‘qlee daliny PPV devivaive has been prepared by Yishino et a 149). jeny L-phenylene vinylene) 27a Yorms & neni Igual [epbose nen ncing. The mates reins is der upon colin Yo roe er ert, ants tend gap (208eV) & menarabhy smaller than in an uneriented imple Ore cecucluminacerce may be achieved by rubbing thin fl of fhe asco induce moleular orenution (50), 12.2. Poy(anthryene vinylenes ‘Te supe uf Wessting rose hs boon extendod by Millen and co-workers i de ‘elep« solble precuror route to polyanthrylene vinyne)s (PAVS) [St It was apt that the energy diflereees between the quinoW and aromatic rx ‘are stractures woul) be dnanished ia PAV slave to PPV itself. An optical taint gap of 2.12 eV vas determined for 1-PAV 28, some 0.3 eV lower than the Nae fscrved in PPV lterestingly, the 9,10 bin slfontu salt dos ot poly- Ineze, oily dust sre elects (Scheme 9) ope BY Setome 1: Spite PAY 23:9) NOH, CHER, 200°C 1.23. Step-Growth Routes to PPV Derivatives, Substnted soluble PPV derivatives may aso be syesized by sep-owth poly- fhanton, methods. Arjene-birphosphiyidenes aj be condensed with TMithaldchydes in Wath fation to yiel altemating PPV copolymers [52 An ‘Roxy subaitued PPV derivative 28 Scheme 18) prepared in Dis fasbon ents inte ong? Ona =385 an) region ofthe specour [5] Palldiuny sedated catalysis bas only been exploited eaivly cece i the syns of subtiuted PPV derivauves the use of aryl drome 6 saan pariclaty mela a i allown the synthesis of PPVs substituted ith alkyl ‘atlr than sikony sidechains, The Suzuki (53, 54], Heck 155}, an Sill [86] re Scions ave been used in the sypthesis of ew PPV dervaives, bu asiing Tigh mulceular weight PPV. derivatives by these mahodolopes hs proved Problematic A phenytubsttuted PPV scr PPPV SL way syaeizct by 3 Kinki coupling (Scheme 1-10) of bromoetere and bis-bevwic acid 30. sab Splint Cpe 385 a) dnd emiiog: yg =7S mm) xia Wee OREIY 12 Pat Apennines Dives AL cee 198 Syn of FV 5 Sues cg: 8 FUP NE, ar ~ «hy, bue-silfied relative to PP is, The molecular weights of this materia) were mosses My~3000 stad Ma =11 830, 124 PPV Copolymers PPV and its alkoxy deivatives ate paype conductors and, 36 3 cmsequence, bole Injen more forte than clon petion in thee mars Eien ink tion of bat types of charge is & preequisite for efficent LED operation. Onc Spyro w lowering de bac: for lectin injetion i the use of ow work faction metal sucha cleun. Encapsulation is necessary in ths instance, bow vcr ah cacium is degraded by oxygen and insure. An altemaive apprcach i omatch the LUMO tthe pone othe work function of the cathode, The use fof copolyiers nny serve o Fees this sve I'ay bow oud tht onal copeywes olen exhibit improved EL. proper tis relive to thet homopolymer analogs This wos demonstrated inilly 0 & txpolymer of PPV and poy[(2,-danethoxy-14-phenyenevinylee] [57]. A var fof copolymers wi iaerapod conjugation hae subscqueny been ves ‘ited by he Cambeidge group (58, 59] and sewer 0,61 Tae tyes of sect copolymem ie ltiely sisighiorvanl A mistreef rmononnat 4 and 32 i plyierized in 8 watcrmethanel mint using sodium hy rox ay base (Scheme 1-11). The ratio of the mits inthe resulting copolymer fay be mampulted by changing the fed rates of movoners 4 and 32. The su fontum groups ae repaced by thoy substivets, and this subsituion occur fence atbeneytc carbons adjacent acting alkony props. Ata cOneauencs, the raslting copoyer 33 consists of many sulenium groups adjacent to pie Tenc omits aa) mostly methoxy subacns neat to diethoxyphenylenc unit Sulfoniue groups my te rly moved with heat teatment of polymer thin Fims, wheres methoxy groups are only parlly eliminated under these cod om A puymer with iserupid ronjupation 34 may be rudy produced. Con fate seneval of rsthoxy substituents acicved using thermolysis under vie onlin to yield te ty conjugate mate 35. “The comgemtion of the copolyner dtersines its cletoluminescece ef cichcy, Opimal efceney (038) wis achieved i systmn 34 when the eed an Stmonomer to wmonones 24 ys 9:1. This represents 3 30-01 improvement Tumincreerce effieny icitive to PPV ib the same device cou (AIaSOvlyimafAl) (38 62]. Copubince 38 has fous ws a waves alScheme 111, Syahele ot gataly congas Fev copayros: yoo, Boe, F300, vata 200°, MONDIAL 2 9) BNO, uO, lthogrophically paterned copolymers (58, $9]. High EL efficiencies have ako teem demonsiraed i akex)- and aysubsituel polyipinytone vinylehes with imerrupiedcorjusation. These systems may aso be syuthesized by the base Indicoddeiyuroalgenstion method [6 "The eftceacy of PIV ny also be rained by inraucing inode ito the polyne chains. The erystalinty of PPV my be lowered by employing 2 adi Fred Wessing method uulzing a rahe ving group (3) PPV pedced by this method fs Beioved Yo contain a inte of ih and ansalkene wits. The tflceney of the teal 0229 when erployed in single yer device Wi 13 Refing the Properties of PPV Malayer Devkes 3 ° pom a0. oer seas roo | RaH.ca oC Scheme 112, SyBest o PPV deates ncpertny rays: 8) KOU, sre atuninun cabo: hs maybe improve to 26 when a dbl yer devo em pine ran maori er enplye Ge Sin 13. “Tarynn hve hechenpoje ie sylete vieylene AB coplyners 38 by ont er of ting « Honea pean Yue of koe and hoes 36 with bsposphonte 37 (Schene 1-2) (6, Perylanines have semathably iow redox poten and Ue cane tramp propics fave beh vested ‘Semiely [65] EL devkes comprsing tines hive domes nt Sivig vege 1.3. Refining the Properties of PPV Multilayer Devices, Any commercial pplication of plyemacha LED wie asim brigh fests high power elficeny, and exlenfel device Wines. These requrments necesite fe net Tor High iin a Tow ving ylugen. The simple sige layer device arhctre described this fr isn n thi respect, ad notable ‘nts have Been mde to improve the performance of PPV.ted EL rats ty the exction of muller devin Such refinement is device arciteare ty five he way for orn Onplys tha can compote effaively with tei ing161 Palgarsene into - Shas a Applica Snisondator Device A hyperbranched polymer 42 comprising oxatianole suai has been syihe= Size, bat defect format in such srclire appears To lint its wse as & hol Mocking material (74) ‘Other elecvon-dficientheieroeyclic systems have also ben investiga as elec tanspertng materi. In parte, devies employing poling ‘toxaline) 43 as an ECHB layer have shown improvements in device efficacy ‘when used in conjaneson with an emisive PP ayer [751 132. Electron-Deficient Polymers ~ Luminescent Transport Layers 1 would be referable wo incre both frscent ad toa aspen op alec earl aed eed ‘mpor layers LED, Rang the aliy of the rly fattest taf ttl lees her thi calcu, than avoning tbe eed wo encapsulate the Cathode It ha bee shown ompuatioraly [76] bas he presen fs Cyn = Stent on the aromatic sing or on the viyene potion of PPV lowes, beh the HOMO and LUMO of tented. The tae fr eecton injection the male ‘ial ert comierty ma enh, However, the Weng oui incompa te wih seongly lesen vaawing sobs, snd anatase syle a ear aa 1.5 nap he Proper of PPV ~ Malayer Devies “y " \ Agee Be, Ca ™ La | _ eee Scheme 15, Stes fC At: Na) KO EK pan tiene ak NaC KO eNO ORME ee 177 es ii in he syne of CN-FPY 4, diahony sabia PA desvative with «cyano sutsltuen onthe vnkne pouton ie nena ‘eles te condensation a wrplinde 4S and tense eee ce Aksatve de he psence oft bane chs cbuplamcnag aes Folasiam terucnke a sient mnareof aeons ae ees {Scleme 1-5) [8h Buh meron are ey ara et sensed ‘he marily be pied by repeated recptaaon, CHPPV say a, en, ela rel and is bn eap BU nn C1 eV] iene sites 25 dalany PPY dress The nobeae wedge eae 6 ate scene fr spew pamriatns he sae Te is Sly slo aces sich an ctor fy ve ee eg a chats Te cleton dicen sate ofthe nna wexeneg yencke lic studs These denon tha he any subd eee Oat of icin by 6 eave eens Pe In court wih conjunc payne, sch as PPV. devs enploying CN PV 47's th enn fan hve ye eel EE 02) wih both cis at suninim cea EL efi et teas improved by sughying a ok moporng yr sch a PPV ieee a141 Pobre vingenes Sass and Applitons wv Semicindacor Devices 1.21 Multilayer Devices: The Incorporation of Charge-‘Transporting Layers ‘To maximize lish ouput, it would be ideal to create roughly equal amounts of ‘bah charge canes, Ley electrons and fois. Most devices deseibed thus fa Nave bon single ayer dvi wher the semiconducting polyner is sandiched tween the cathode and anode Khas lveady been mectione tha PPV fas gher amr for cron ject dus for bok jection, and lesa peeren aly injected in a single-ayer device. tis common, therefere, to we aditional layer of materi oenane eloctron injection. These layers are tered ekeron- Condecingholebleling (ECHR) layers and the configuration of typical de- ‘ice incorporating such a hyer is depiced in igure 13. To work cficeily, the ecu ainty of te ECHD Layer ma be higher than that of PPV. Tn sch a tse charge caer recombination takes place avay from the polymer neta ie fice, which ie known U0 act as quenching sie. EL efficiency may ths be coo ‘ray imgeoved relative te singer devices. "The cares! ECHB rei sued were the oxalazles, These ar electron eft telah and 244-biphcny ll) 5(4 ert batyphny)- 1A onan (WD) 39 was the gt member of this las ef compoutds to be wed weces- fay na sind fim EL device 10,671 The materia Is avaabie in high per ity, an ay Be nad spect a a persion in polynety] methaery= tac) (PMMA) (68), Inay ao be blended to good effect wat cktrlumincscent pubymes [47, ©, 20), although iis petened to deperse PRD in an insulting Felymer such as PMMA to overcome potetalprblems with phase seuratcn. Fao increase in deve thickness an teviale consequence Of mis appr, fan this afte a8 se in diving voltages in an TTOMPPVZPBD-PIMAT Gi dovce, This disadvantage, however, is outweighed by a rie in EL efficiency fron 0.1% (or an FIOMPV AC Sovic) to 08% (for TTOUPPVIPED-PMMAICS) ° ECHD Lave at eg8 Pe? ® TSE ten tie sls avenue cre PUTT be nis ‘Ginn dys pan cee PV eral acy Wha 15 kepuing We Properties of PPY— Muaer Dences 15 ‘Scheme 1-13, Gx of oudarolecntanng lc tarsperng mao ecton hopping isthe sain change tamport mechanism io ECHB meri There is precelcac inthe potocondictsiy Held Tor improved cage transyont ty menporieg a unber of eux ses tw We siate nclecule: A vamber of a {enots 10 adapt tis approach for ECHB materials have been document. May {eine oracle cere the electon-tanspor moiety and example include Tadlene 40 and dendsier 41 However tess newer systems do et ole sii {Ean improvements in clacton injection ver the pret PBD. ‘An ahematve approach wiles paymcric analogs of POD. The oxediazle nit may be it the polymer main chain ov altace a aside chin. A resonable tdviee performance hs Been demorsrated in po(aramatc oxadavoks (71-74)181 Parle vpencs Shei a Apis Secondo Dees Bie, yet ‘Sehame 116. Cole tage ae er CH PV daratnes the highly slectondeficieot CN-PPV. The inliiliy of PPV may be readily exploited inthis context CN-PPV may be spi eaaed onto layer of PPV and 3 fworayer device (TOIPPVICK PPV Fetes, metal) funchons, wh We. (4st) intemal eicienies (79, 80 Unike ther two-aer devices dicted pe Vous, esson in FPVICN-PPY two-layer devies appean wo occ exclave) {oom the CNDPV layer Ik mye ponte dat CNPPV behaves se» snk for exctos and charge caries esi from the PPV layer isa unfaveued ease: ‘quence, ‘The Knoevenagel condensation roule w CN-EPY may be eal tailored and several denvaves of weyano PPV have now beea symeszed (Scheme 1-16) {G1, 81} Many of thee ako stow high EL elficiencin wen usc in double- layer device configuration wih PPV [82,83]. A representative example 6 MEH CCA-PPY 4, which exons very high EL device efficiencies inthe redlrange se sion of the spectrum. A deuble ayer device TTOUPPVWAL produces red orange {COO} light with s huni efcieney of 25m" [6l, SI) The emnsicn olor may be allorad by meijing the subaiuonts 09 the pelyner backbone Bulky sbstituens such a the isopropyl group of 49 case a wisn ofthe ply ner backbone, ducing Oe ait ts emson spectrum (peak waveknzth Siam). An alternative method of reducing the efleaive conusaion leash ia these systems isthe incisporan of mets hnkages. Polymer 49 ents i te bh ‘gion Of the specu, Sbsatation Gf ons becca tng rl a thiophene 1 150 reduces the band gap ofthe payer vo 1:75 eV (740 nm). Emission in thei fed ws int demonstsed in an TTOMPPVISWWAI LED (3). The emtston ma imum may be redsifed further by the replacement of the second benzene ng ‘wih thephene: Poymer ST haya banl-gap OF 36 V (R00 uy SI, 43) 1 Refi the Prope of PPV — Mater Doves 19 ‘Awetnent of electron wihdeawin sents an aleraive sppreach to polymers with a hish eeewon sliniy. The Wess Ing. procedure ay be exploit wo yiek! poyinem 52 and 83 Wi olde subtinoats ce the sng (86) The group at Cambridge has ayenzed holcbloching desivatives such as $3, synesiasd by bromo precursor route [87], oF 54, derived from 3 Homer poycondensaion (88). Me halogen subsitued PVs 52 ad 53 emit light inthe sed region ofthe spectrum (msn maxima {620-630 nm) (86, wheres the tilucremahy) denvative $4 was found to emi yellow light (510 570 nm). However, the PL and EL quantum eliinein wore foor in these mera A double-layer device employing PPV asa olen UGjer and alas a cathode achieved an intemal Hi eficteacy of only 0.00% [87 9] Wi ikelytherefone. dat hese materia wl be more useful as BCH layers than esse byes Phe poe Pu Py, Seneme 17. rgntecten anna) FV danenes wan ecto nimaerg gps coe 1.322 Hlectron-Deficint Arumatie Systems Pyridine is considered by ganic chemists 0 bean ekzcron- poor arate system an pyatine sales PPV sich 2685 repeenl a ltmatve ope oie the clcren affimty of conjugated sysents (Scheme 1-18). The material ay be syhsied ty palamedes Sule aoplas of12-be taut) Cihylene and 25-dbvonopyidne[90| The polymer i yielded 3 an one pow ‘Ger and is soluble in cro, emis inthe ted rego of the visible spectra (500m). The matal ony be allylted or prtonsted st stogen to yW) solu polymers $6 and $7 respectively. Nalkyation induces a bive sf in emission 0 $40 am When butyl loup i append tthe postion of 2.-diwemopy Sin de resulta poly poly Sbaty-p-pridyvinylene) SH is solble i com ‘ational rane solvents [1,92 ls emis spectrum i ed sfulled conser sy to 630m a 3 device wi the configuration ITOMBU-PPyVAI hasan exter al quant elfiiency of 029% [92] Pobjmer 88 exis as three diferent mpiosomers: head0-nea, edo ea and random, The various sess have been sjeszed, ad it has been found they have diferent absorption, PL, and EL spect [93). The elective conjugation201 Polarlne vine - Sens an Aplus i Snicndcer Devices Sy, dh, ch, length of the ead-oeal omer ts found 10 be the lenges. Its erision spec: trum i minal 8 65m. wheres the head-on random owners em a ‘364 nm and 375 om, respectively [9 Polycyriiae vegas) SS may aso be prepared by she Wesling route (Scheme 1-19) [95] Fully conjugated material ay be cbuined by thenmal clini ‘ion Of the sulfniu sul 61 or the hale G2. The method, boweve, ooes Bt 14 Fill Color Displays The Seach fr He Emirs 2) Yield 2 material of pricy high molecular weight (ca. 2500) as is evident i -MALDI nue spoewencopy ‘The HOMO-LUMO band gop ofthe matt f est mated to be 222V, wheteas it eis inthe crangeved gion of the specu 3 UV." ald nate PL quinine etiemy 2) camcalaubly heee aw Served in PPV (2%). 1.4 Full Color Displays — The Search for Blue Emitters ‘A snus colr display requis the tree primary coles ~ red, green, and bie - and these exons need to al within the prance defined bythe CIE cox: I96). Blue FL has bee the slowest in developmen, both in tao inorgann ‘aerials aswell a in polymmen There area mune ofcifferatspprcches to Stuible polyneie anal. It hax aleady bean dacinsed in Seton 1-2 ow th, HOMO-LUMO tap ol PPV nay be msl by insomplce conversos tothe Fall onjugued poy, Fanhernor, the band gap may be intesed ty appending Stencally demanding side grvups oa the polyner mai chain. The wel op lect propery ot prenytubsttued PPV denvaives has alexy been Os cussed (sr Secuon 1-22) [42] The following section wll enna a umber 0 ‘ther approaches to meri hal crt in the blue region ofthe specu, 14.1 Isolated Chromophores ~ Towards Blue Emission ‘A aleve approach otlesing the bund gap ofa polymeric water involve the use of polyncr blends. The blend of a Tuorscent dye in ab iat polyme ‘avis ye 4 polymeie EL marl with useful haniecent characters. prction, however the fasercent yield in ach Mend fe vey lor 4 ose ‘quence of the lew mle fraction Of the luminescent species, Devie bigness Tay be enanced wnsieray by Ue He OF an eAEUORTNE Polyne, e, poy (ity east) 64. The imporemiat ia perfersance manifests Hell even 3 very low concentrations of fixrescent species. Alemativey, the active chromo phore muy te incrpercd into the polymer backbone sll andthe lightening Species canbe spared by varying lengths of ine spacer” unis. This has best Semone the preston of eopymers suas 6. These ae pepe) endocting a Wiig condemston of isle nthe qwesence ol Way Sian of Surat dadejaes (Scheme 12) 197] Mat pest ctrl oer the etiaon ctor ena be achied by employing couimela quunties of 3 bxphophonium st ef. 67 and a alee contain Inga exible unt such as 6. Tis approach ius been exploited by 2 number ct rescachs [98-103] The envsion wavelength of thse miter sn he be Fiuegeer repion of spectnan (470-495 nt).221 Potferylone ayes - Sess und appcatont i Sencar Devers GB Owrash, Sehare 1-20. Pin cabana! exampo ofa payer wh an ed come ime o- ett Schome 12. Sts of a theo coplanar with Koksed cromcpere by Viti yearend) 142 Comb Polymers with Chromophores on the Side-Chain a aide “The luminecoet moity may aho be aac the polymer tackbone Chaar, yeding a comb ply. this stance the main polymer chain is ofien Sc he ren wih medal ml tra ney te ennoyed. Ditenn has prov 0 fe 2 wl amor i hi com UGar ihn ten tcl vo ayo sch eg ee poring dials unt 7,103,106). A ioe LED evn PPV ws Faietrampering layer an 69 a an emiing her showed erent he ‘zon (257m oft apc wth effeey of O07 tal into dhe ye Tewrgyeen raion of the spectrum was ctneve, an this was attibuled Wo ems- ‘on fom PPV ill Baar gore roe Po fe Scheme 1:22. ares ecnhunnescert pene wih sid chan dpe. ‘The precive contol of ROMP methodology his teen expel ty Schee ant ‘o-werkss in the polymervation ofa nortomnene moncnc func wit sisyrlbenaene side-chain 70 [105]. When eslcium is used sx a cao, an eke nal device efcieney of 0.3% is cbsrved afd the peak emission ih te he IS em) 15 Chiral PPV — Polarized Emission Mais and co esker [106] have ecely reper circularly polarized elereluni- sescenee (CPHL) ining chil nonjupued PPV denvanre ML eae a Sich a ys he sbserted and ented Tig he eee eons fe sedi (cecal pelted compen To imypene saleby paper ek 4 and raenic oer: kad to be eoplrerza. Small thi scp formed these seri as consequence ofthe sepionpeif autaisanes aces241 Polyasen vig Sys and Aypicons in Semicon Devices { aa ae Pa a Schome 123, Cepia PP devas. the cnasiomescally pure sie group on the chin, Tha conjugated palyner ‘bane maintains its onic Chirality bh solution and soi lt, aa eeu- tary polarized emission equi no external marescopc ering of te Cac hore: Faeroe it wae found that the civular plaizaion in absetOn Ran Sho ge nan apgrgate solo than soi i, suggesting farther orig, ‘rpalymer cme nan appropri sven. The diymmetic ight cmt yer {consequence ofthe polymers coositution, te solvent andthe process, cond ‘to employed. 1.6 Poly(thienylene vinylene)s — A Stable Class of Low Band-Gap Materials Polysetylene is considered 1 be the prottypical low bandgap palmer, bu is Pott ts i device ica have bean hanged byt smstity Yo both fnypen and mostre i ws pine and doped sas. Poly(hinylene vinylene) 2 fh boen extensively studi! because i shares may ofthe useful attiutes of flys loon fur show considerably improved envio sili. Ths ow and gap of PTV and is denvatives Feds lf to poteatl applications in beth is psi sn highly comstive doped sate Puthemnor, the Vinylene spaces between thophene ais low subsittion ow the tiphene ring without dupe ing the conmapaton leg the polymer backbone Polymers such te PTV Rave potential applications a the ative semiconducior layer im i film wansstors (TFT). 16 Poyiiowtew none —A Sue Clas of Low Band Gap Maries — 2 1.6.1 Organic Piel ffect transistors (HET) ‘Omaic musa have wecly shows promise a the active layin ric Seto hf wants (TFA). Suc doves have psc! apse th Switching ema la panldplys and sat cas Grp natril col fave susan cost avanages ons tir sileoncaumrare if fey ean be de festea om soon, tin css the es) Toba of Kies, est (plas, The geomdey of 2 Opie thf iamsater device deisel Figure I-4. The cure psing Deween two cede, We strc ab da Re ae eee ae pee eee ing ayer canes the cient and the prfomance Of the device very me cence cnt mud, yo he seaonaucung mane. Ape ue tren the ONOFT rat af he Seve; ely he semcoctg layer sil Wet igh ickeleet mbit Cale son ss ‘eran oes em cy tm malin of th * fuiee ales ie suc! for the sada applic cheney [07-112 Cu 113} and pemacre (114), Mabie be & Tenr'V' sr hie teen sine with ONVOFF ras gest tha i ‘ne ule wow eed by mination of he mmeoncing Inger Ato tive pect lice ow tana conducting Plymers poten i) tec) 2 nye mobs of Oc? V-"8 113} bss tectog ‘ful remain before thee deves nuke ol 1 mark. Syathste apm that yield welled repnguerpytcphene cr pobre vip Sormies mayo the to po of onganic mar seman devces| we ‘Stunde gc th sa yt sto ae ee eae S'n The ainen dene nm yt sy eng be ‘Sipps26 1 Poa viens Sys a Aplications i Senicontuctor Devices 162 Synthesis In common with PPV 1, however, ret PTY is insoluble and infuse, The mote: ral was ft symbesizedin powder ors by Kossnc wing a Wag polycondersa- ‘ion matbedogy [16], The fit example of PIV syetheszd by 2 acuble pre ‘ser foute was publshed by Elerbaumer and co-worker [117] Once agin, the ‘Wes edo was expla (Sete 1-2) 25 Bieta reiiylibionhene chlerde 73 war tested with one equivalent of water at O°C and rapidly formed a thick polyelectrolyte. The material may be cs fom aqueous “aim set conor rua PTY by heating to ISOC. The ail exits com ectvy of 60 Sem wen doped with fy. The watesolble recuse polymer, however has a tendency o gel or prcipia during dialysis and sone. Funes mor, the soluble precursor prone to elimination even at room temperature. The route was mnoiiod somewhat by Musas [118] abd Sito {119} by ue the Sersolutie prcuner wh mthaol. Ax 3 comaquonce, the slfoian groups Iie replaced by soy substisens tendering the precnor ply 75 soluble fea solseven Thea eset st 200-230" C ihr sniy Matera ih 8 lage absorption centered around 23eV (540 nm) and an opel but gp of TBA ate tn of el hs ten dwt om tha oases [L201 Wha he fel te eatin hes care ft im we, that Tow temperaures are benelicsl for high monomer conversion aad pelymer focesiilty, The optical anouopy uf PLY won cxananed Uy ches, Mims f thickness 0.1 je (121). A redshift in the absorption peaks on the. til wis observed upon secking indica exe bighy ordre polymer ins 'A drnuback of the Wessling methology, hours, fe tha tae feats of cid catalysts are retired To completely ciminae the methory group. A corse aR + GBD 16 Pabyiianlene vgn ~ A Sue Clas of Law Ba Gop Materia — 77 quence is that this syethetic rue is ot paricuaty useful for semeonductr Stee application. A eoute employing 9 saiue plecuror has been rely Ge Send bythe group at Luce Technolog. 163 Aldol Route Part peiythisnylne vnglene) hs abo en symesiad by an aldol prune fonte [122] In this method, S-nethy-2sbiopenecarbalachyde 76 is tated with 4 usc andthe monet pelyusien icing ycearar 77 wich is sible in trate Thermal eament ivan ack solos at 80°C yields che fully conjugated ‘hata, Alleratiely, the slid polymer ay te heated to 280°C w effect cin fnaton of water Fully cnjugatl material cake How conductivity (H* Sent ints pristine sa we Edo +. DL C)-ovo4 | O~, ‘Scher 1:25, el leo PTV 8] KO, DM, 8) Ret 164 Ring-Substituted PTV Derivatives “Tee have beeh & numberof dre syste pyrences to substiated PTV Astivtives proposed in the hist decade. Almost all eeu onthe sfomstic ing 2s the ite Yor sutton, Some elfor as been made to apply the tatonal bse fstlyct debycroaligenation routs (0. PT and ie sabwatund analogs. The ‘methodology, heweve, is nots succesful Tor PEV 2s its for PPV and ts de Wes hecase Of the gic tendey forthe polyectiore Magis) recunor Sontansaaly 40 ciminle at 100m temperature. Swaper and co-wowker {ented ths Youle fo synthesize 3 FTV denvatve substtited wih crown er ‘with potential applications 389 sensory meter Setome 1-26) (123). The sym ‘Ss employs Fagor condensation (124) i it ntl stp 1 yiekd dol 78, Treat incor wis ohosylae yields cr ther furcuonslized duophene deter 79 “This may be clsboraed te diclende 81, bu pure material could not be isaed And the ihre mbnomer Hd tobe polyinataed tn st. The polymer wosed28 1 Polyfarene vinyl Sythe ad Aplications i Semiconductor Dees iat aie afi = on Tee ie k fo ees “Ay ofan Scheme 1.25, steneted ayitece of @ Gow ebechectorakid PTY, dorvaive 76 Sy ROCHOHOLO, Coe NP) LAP IRE SO Pe, THF) ROB he sowed solvatetvonse teaver, but could not be reissolved when slvent was ‘emeoved, andthe material could only be charaterized by IR spectroscopy. "The fist substiutod PTV derivatives poly(-mnethox}-2,5ahenene vinyens) snd poly(-thony-2.5thienylene vinylene) BA were syusiz by Elseaboumer inte lite 1980s [125]. The method employed was stop-growth condensation gece reece eae tichlorcthene (Scheme 1-27) The materials cbained were deep blue solids, but the majonty of the semple was insoluble sn common organic solvents. Epdproup cnene 127. Spec shy PTY canines on Sng PIV 7 3) Bal HGBTE.0°0 ethers O soem, cuenee 1 OCH-CHO Cogs NEM 16 Poyiinlee viene A Stable Clans of Low Band Gap Movers analysis of the imgoluble proportion sugusstd that the number averge melkcule swaght My vas over 9100 haa. The clue pation, However, slowed weit Tig optocierwenie woyeties. It bis an absorption maximum of GOD mm and i bund gap of 1-5eV was signficanly lower thn that of PTY isl. tn adéitior the polymer coud be eat att thin fins. The eletron-donaing groups are be Tied wo rede the ionisation pofensl ofthe polymer considerably compsted tinubsituted PTV. The men! could be ail doped by FeChy ant prsed pe tes of poly(-ethony-25-heaylene vinylene) tested with FeCl i nitomethun sélution exhibited conduetivis of 18 en 1126) Mine mit yr mute man cnpleyed by Blan and cowoskers (1271 nh synthesis of poiyG4-dibulony-2Sienykee vinylene) BS. The alkoxy chair Hidp wo solute the polymer m convenonal eganic solvers ad this con 2 veandhle esti ofits molecular weight. GPC analysis of the polymer si igs Ny 12400, comesponding © 3 degree of polymerization of 49. The ells {he conjgaion Kegih ofthis mural an improvement over pol batho: ‘oihenyene vinylene) the absofion maximum of ply(.tsbutory 25-4 ylene vinyl) 45 sed sed i> O07 nm with a shoukler 670 nm ar ‘lathemeate. the color of the mieral could be reversibly changed from Bie + rely transpirat ia 8 doping-dadoying cycle. The essed candi of oped moter however wan ofthe order 1 Scat "Tn methodology hes boon Torher extended wo hexyksubsinted PTY deriva by Starahawa era [28 A repieregula polymer consisting of esi vinyl sud henp|-scbtiued Uoghene ums 48 vex prepared by nickel aed eros pling (Scheme 1-27). The dpe of pobjmervation was moderate (M= MAP nd ihe efective conjugation length ofthe mutrial A, =470 om) was Cons bly shvier than ebscved tm porons PTV or is dislkony-aubsttued deivtin. ‘Thm x ably © comsicne of the inercaed strc repulsion between tk ‘roup a the Iytgen tached Wo the vayle exon. “the cNuny coupling rte us been tlsed Dy Twas ana co-worker» the syntbeis of PDRex TV AS (Scheme 1-29) [129] Dialdehyde 90 is poly. isd m the presence of titanium eracloide and zie dst. Molecla weights $3000 are repented and the pubmar fos soluble in solvents such chloe form. The epeted abortion ian (605 nn) was close wo that observed the Blok route (127) “The Stile action hss eon employed by 2 numberof researchers inthe sy thesis of soluble PTY derivatives [130] Alytsutstinated PVs were symhesie sete 128. Syren of deny PIV cenaves: 8) Bui, MyBte EXO; b) CH=CH Fchieppe) Bs Mery THE301 Pabanlene vnenes- Sythe wel Applications i Semiconductor Devices ay EG Seton 128 Mey cv ode ony PV 78a Bis, THEDA Et Ty Ba a My Reatyt Scheme 130, Sule role te alyfabetiund PTY cotvaties: e) 4, HOS b) BUSNCH-CHEeEn PAPE NON. by the reaction of 1,2-istibutytannyl cthylene with a diiodttioptene 91 (chet 1-30). "An stative row to dslkony PTV derivatives his recently teen repent by ‘Ekenbsuner and co-workers (131, 132). The method employs the them elimi- ‘ation of sly! group fom soluble sulfate precursor polymer (Scheme I= 31), in addition, the aubors claim the fis wolation of the quioreshige incr ‘medic nod eherctersed it by "NMR end msn spectrometry Dibatony- PTV pro ‘ced by this methatology exhib a signticany smaller band gap (12eV) and higher inocu weight (a4,~8700) than ihe same nudenal obtained Dy ether methods. Poly(4-dimethoxy.2,Sthienylene vinylene) PDMoxTY yas deep blue in colee C680 m) and eabbited & condicity f 25S en" when doped ‘with FeCly This mated is xpeclly saci ati acide the ee oF anton ctl catalysts, which ae potential cemtaninans for device spplicaions. 1.65 Vinylene-Substituted PTV Derivatives ~ Tuning the Gap, There have been very few examples of PTY derivatives subsiuted at the ving: lese positon. One exarple poly(2,Shienylene-12-dumatboxy-thenyleac) 102 Ju Deen documented by Geise and’ coworkers aid its syahests is cuined in Scheme 1-32 [133]. Thiophene 2-dicartoxalaehyde 99 i polymerized using enzo condematien; the poljayloin precunor 100 was tated with base to ‘obtain polyianion 101. Subsequent wetment with dime sulfate ards 102, ‘wut fs sluble in solvents such as ehiorfonn, methanol, and DMF. The molar Inass of the polymer cbiained iy rather low (f,=1010) and is bend gap (Eq=213eV) is substanially bleshlted relauve 0 PTY isell. Despite the low Ea rea ae erates SR, 148m") Pe ee es Der, + AR Cet Scheme 121. Sarbaumer role i derebony PTY 92: a) Mo,S04: 6) LAM TH ‘sh Zl) MCHEA CHC eX THE. 80 C. DB t+ a Geo 34, Scheme 192. Stes ct 96) 8s, TMEDA, DFE) KON; Bu Kot Mey, 1.7 Conclusions and Outlook “This survey fas demonstra that the field of conjugated aryene vinylene pol ners hin matured comsieraly ‘over the past thirty year. Several syne rgeorle tn plntopiene vinycors ve heen developed many res allow saluion casting of polymers mitra thereby Tasting netrpwaion321 Palarsene viene Syste and Apictins Semcon Devices semiconducting polymers into wal devices, The technology employing pod (Grjere vinylena}s ar the ative layer in LEDS haw advanced comnidonbly over the past en years, ad the impact of controled sys em device properics can ou be understate. It pstups at toy that PPV derivatives have hd ier impact wo date inthe eld of mokculr eectonies, but esearch efor ae Extinsng to devise new syheicapproahes to PTV and is derivatives As 3 orsequenc, its aniipated tht nove applications of such low band gap men alsin soldstue devices will be pursued wih increased vigour i the next de Acknowledgerents ‘We thank the nginecnng and rnyscat Sciences Kesearch Counc (UK), the Commission of the European Community (Marie Curie Fellowship © MMM, sd Cambdge Display Techookgy Tor fnancal suppor. We acknowledge the ‘allaboraien in Combate of our euagues Pol Ie Tvicad, De 5.C. Mera, Dr. N.C. Greetiam, and Ds F Casal and we thank Dr. A Kraft and Dr. A.C. (Glussdale for thei nee in his Work. References 1M Siang £4 Ls A. Mita CX, Cig A ep Chen Sz Cha Li Beraies DC, i Rees BD. Bader AR wn RN. Ma Mak RL 2 3. RUA West RG Zinmerae (Dow Chom, 3, 1968 Chom Ae 1965, 6 1. fee-Sman Wb Facer DL Gi im Chm ee 119407 1 F Lowel, D. Vso, Gein, Sy Met 1985, 9,50. 1 Lever Beane el tn Mares 1.26 7, th BSR nee es dg a St te DS e188 6, Keprnces 33 esi M. Kab Ken Chan La 198 197 Onde Spy Sth ee DG 1 Rete Tsai KL Pc Gna Wi, ale 186, 37307 Yes tun a Ci 3 Such fama Aichi Ob Sat Ae 1998 7. Bie AE tae ie eee he a Rage A ee Mier pes en a ni nm Serna nel eg e atiniea oe eA ade eer aaa eR Ae Tita Gi Sri Par, i Fa A an, yh i 198.339 D. Br 63, Sa KC EDs CL Tikken, YA TER. Kes, AJ. Vow | > geese teen es eh om mu NIN Baa, DG, Hl: Obaen, JF Fema, Sait Met BB a |S tga 11 Meter. Sead, Wad Chom are I cae Can Hoge, K.P Wo, (A Mesa 1 mn Maer 194,245 IM lamaguei, Keo, we App Pls A9AS, 2, LATS. Mt, — 1K. Yoshino, me Appl Ms 1006, 31712, poi menvaetaemte nh E ech, wi ew, Marmt Chea eS Pec Mie Deas PL Bun, AB Howes, A. Krak, AR. Bown, U.D.C, Bralley, RH Poor, Moser: Aes ee a ae eal hala re RA RD brs DS ete Ak See STR A ETE leet. , ae yp eeeneh ie pepmennts ears Nik ee east eriparsre p Hee 1 Patfarsene vpn ~ Ses en Aplications i Seniconduser oes ‘oP Bay A.B Ham, DDC Bae, AR Brome RH. Fi KW, Cyne, Sat ti Se S'S A Dattatger A Lavine ME Cli, Scene 19952, Hof Aouad S Pier WH Heel Sy Mer 197 20. EM, Boney Fon Rent Bae Chen Pi. 99, 96 276 CMa’ hs Shs gps et 1873135 Aaa’ Tk To 8S Jl Ph L208 ‘Ri Bron, DD ey 1 Burge a, Gea, PL Barn, A fies A Ap Pl: Lan 188 1 288. Nit Aah ee, Fes J App arm Cina Og, M, Aeron, a Mae YE. 7 90 Yan sR At PPR 7 f Gecieae Mem S na Foch, LW. Sete Sige WKS, moors Hate 95,2 9. hac Dat Keg Ry, M. Gea Sug W Ren, Sa Met ‘9a 7095, Thoma 1.6 Dea Mea Ma fly: Sp, P Bom AT Dignan 16 Lay BC Gad oe Pe 88 8 Tay A Hc Ch PL 983750 NC Granta SC thet DDC Bray, Ri Fen Hl, Rae 1B, INC Gsm, Cc, B.C. Bey. LHL Feed, SC Mth, AB ols, at SC Moony DOC Bray, KIL Foe, N.C, Grentum, A. Hees, Mat Be, Se. SC sr Cavin, AB. dns, LR. Baigent, KL Fen N.C Gren, 3: Gin Dik tapae NC Geman 1 Gai, RN. Mala RH. Fae SC Mor AB Nee at er tn 67 ISIN Ha Oe Bag, Cath, NC Gast, RM Fen S.C. Merah, A. DIC Eugen Fd: Hance Ri Pid, SC. Maa A, ths, Sh Me 185 71, BE Meat DDC. Beate, R Cav RL Fen, CG, A Ht, Pe Src ws 48 1 FM Ga, AS PM. a, BH EE Kann, Macnee 1986, 29, <8 RC. Guumie 30 Li F Cea, 1 Gane, A8 Hees SC eh a, ‘Sur, 85 Rita ABs fie Crk, AE Da, S.C er 1 Ge, Cal fant ae 9784 35 (tan 8 tla, 1-6 LAC. Gm Dai PR Ray, Can FCs SL Manca Se PoP 9923116 Tum €-€ war ME Munn Summ RA Regie MA, Man, 9. Soper net HOE Tum, LE St BA, Rg, Chm Mane 157,30 se Sing cae. Se, MCs FL lone An Chem Sa 195, 17112 ry refrmees 9 Stee Sa FE Ra Rts we 1 ng eu, rr 98.26 ime 8 ewe ie 1 Se vn CS 1 gga Bi fu om i a he ns {pcan MPT Chau, amen, HEM St PLM, Dade TW, Megs EST Ah am seek a Ge Ee sues aon on ‘A Dh HE Ka, Ts, KH, Sere 19. 264 1 Se Ree Rene eet a eter en (ecg a elton! 94 ena ae Cb, Damerognin. A Henwn, A Pun At 196, 8201 Gere fam tt at Me ihe Pier uicade tanec ire eet tare lee ome i ue ee ere ee a HSE Se Se, Be eae LR a ga mo u Te Wd Marca TO Swag Pa Py im. Cn Sor De. Pai, Che, re Eh fa) Am Ch Sac 198.6720 i. ES Ee, uP Bs KHOR Sa Sapa loc RL Ehsan, m= Cow AIL tit) Poh, PC sa Dt acca 26 2108 A ens e Al H Stan Some 9 Ste a Cae Ee PA {1 Gi Ri Ene JC Se Chen Ca B98 3 TERR ncn Bn ge fy 1, ib Poe 1983, 50,2 Oligo- and Poly(phenylene)s Ullrich Scherf and Klaus Miillen 2.1 Introduction The structural regularity and order in polymeric or oligomeric molecules play a critical role in determining the physical properties of such electronically active compounds. This creates an exciting challenge for the synthetic chemists; with the emphasis on the physical function of such materials, their properties have to be selectively engineered through synthesis and supramolecular assembly. A fruitful design strategy is aimed at controlling both the microscopic and the solid-state macroscopic structure. Qn the microscopic level this concerns a homogeneous chemical structure (configuration, tacticity etc.) and, on the macroscopic level, the solid state morphology (disordered, amorphous arrangement of the molecules or a controlled supramolecular assembly), ‘The synthesis-driven approach towards material science can be applied to cre- ate oligomers and polymers with optimized properties, e.g. maximized carrier mo- bilities and clectrical conductivities or high photo- and electroluminescence quan- tum yields. It becomes obvious, however, that the ability to. synthesize structur- ally defined r-architectures is the key to these high performance materials. Besides the ‘classical’ search for linear, one-dimensional electronically active materials, synthetic approaches are now also focussed on the generation and char- acterization of two- and three-dimensional structures, especially shape-persistent molecules with a well-defined size and geometry on a nanomete! le. It is there- fore timely and adequate to extend concepts of materials synthesis and processing to meet the needs defined by ‘nanochemistry’ since the latter is now emerging as a subdiscipline of material sciences. 2.2 Polymers A large part of organic and macromolecular chemistry starts with the chemical functionalization of benzene, and benzene units serve as building blocks for un- portant polymers. Naturally, benzene- aromatic materials also represent an important subclass of z-vonjuguted architectures. Despite some synthetic difficul- ties related to the generation of structurally well-defined oligo- and poly(phenyl-382 Otgo- and Pohiphenenes «te both academic and intial racurcters have hed constant interest in pho nylene-type material Poly(pphonylene), PPP, censtiute the protorype of righted polymers and ‘ae curently being itensivly investzated (1 The key role of PPPs follows fiom ther conceptually simple and appealing’ molecular stuctr, from ther seme! stably, and from thie spent phic propre [2] In tr, this is the result of important advances made in aromatic chemistry over the Tat few yeas. Te folowing secon gives an overview of the mem cmos mls 4 severe polyp-rhenylenes wa different symetic approaches. fol =: ‘ewubiuted pont shenslene) PPP 1 a a paret system of a whole class of polymers a0 insoluble and ntactable rar, avaliable by 8 variety of tote methods [3,4 The lick of solubility and fosbity hinders bth unequivo cal chirctraation and the processing of PPP 1. Moreover the intctablity of ‘Gaunstisted PPV matenats has twaed ay Serious commereat doveropmee Of te polymer. 22.1 Oxidative Condensation of Benzene Derivatives ‘Tue fist anemyes © generate poby(rphenylene) (1) were undertaken in the 1960s. Kovacie et a, (3 reponed tht the oxidative treatment of bunzane with copper chloride la the presence of song Lewis ack (aluminum metonde) ‘ves rise fo a coupling of the aromatic rings. During the condeasation reaction fadical cations are formal as reactive intends. The maximum deprecs of po- Iymerization ae ca 10-12, The benzeve subunits awe pelereaialy connected in the L4-postion, however, croslinking and exidatve couling to pelyeyelic aro- matic hydrocarbon uring blocks occur as se reachons. Adapting the nit procedures of Kovacic ef of. her Isubsiaied benzene derivatives. were ‘Coupled to poly pnylenes Hetsye oat 5] published the onidative coupling (agent: copper) chloride! slurinum chloride) of electron-rich benzene derivates such a 2,Siethox)- tenzane to poly2,S-dinethoxy-1-phenylene)). The resulting plyuer only soluble in concentrated slr aed, ands fusible at 320°C. Veta ea. {6 de ened the coupling ofthe sine moaomer with en chordeminum eho- {ide The polymers obtained hy the suhors were oot Heroughly paru-tnked 22 Pobmers 39 feist Yoshino era.) prepuce 9,9-subsinued poy(lvrezes 3, in which slubilc- ing ay! substituents ae tached atte metho function. The soluble and fst be poly(9,9-dir-hexyfluorene-2,/-ybs (3) are abained by oxidative capling of 99-demheryluorene with rend) chloride and ate characterized by murder average molevlar weights M, of up 10 S000. The longest wavelength ebarpion ‘masimim dy Of 3s ceaered at aboot 388 wi Thereby, yt shifted batho bromiclly Bp about 30 nm relative 10 Ut of the pared PPP stuctre du 10 4 pri planarzaton of tke PPP-ype polymer 3. Pe es ‘Sereme 2 ‘Tamsition from the purot PEP 1 wo the polyfscrene) derivative 3 touches erica aspect of poly(phenylene)chomisty, Ineducing alkyl o allay subt fet can dramuticaly nance selubliy while atthe sie tine inrding ne fing torsion and ds inhibiting extended x-conjugaion The tenykne uit ean be tegardd as a tridged and plaranzed typhenyt moi to which one ean aac allyl subsients without ecating steric inhibition of esance: Furr staegio ined at suppressing the mst dntortion of atorttc subunits in substued polyp-pheryieney wil be outuped Dw, ou Metal-Medtated Couptings Eatsies to the preparation of structurally more defined PPPs have evolved based ‘numerous synthetic principles of organic and orpatometalic hom. The svailablty of more elective, pre recent methols Tor the aya coupling sina molceule represents a nyponatt driving free i the develope of ew Synthetic statics for poly peuple aa eter polyarylene In arcu the Pu(Oyeailyzed ryan eauping acconling 4o Suk [8 Cayboonie aid402 Oligo and Poypherlenei Pls ay halide o tosylate) and the nickelOycaalyzed or mediated coupling 3 omting to Yamamoto [9] (ay halide oF esate plus ay halle ox osslte) Ihave Been mest succesfully employed. “Typically, such reactions were designed for the symess of tow molecular weight onsie compound the, alice havng prove the syle Foti, ‘ak show to greatly improve the chemistry of eonugued polymers. Pie 1 void side reactions suchas dehlogento or debe Othe Tuncoalized ‘monowersoflen eretes, however, an unbalanced schol ad iit the {Ginabe molecular weight ‘Kaciyana ea [10 ported cn dhe NiO)-caalyzed coupling of 1 4-ditromo- 2x payatoyetypenyee) a 9 fprcunor 4 was then saponified to catoxylsted PPP & and thermally decaboxy- Ete 1 vith CUO cally However, due tothe ban escon Candin. the fra sep, the reaten canna be cared ut satisfatniy inthe solid se i "The sniegy of Kariya represcns walle print rte a was de veloped to overcome the characters shoromings slut, ack of proces {ity of previous FPP syateses The Condensation roan came Gur wih Sokbilzed nrenomer. leans 1 3 soluble polvmerie itemedige. Inthe final Teicton skp einer isdn comered, poral i the sod stat heen of eee ee gates er amene polyenes) t= ‘As as bon etlized above, a second, very ful sytetic principle For obtan- ing structurally homogeneous, processible PPP derivatives involves the preparation fofoluble FPS wa iodscben ef soubuuang Side groups. Ie proaceng Work hore is cue out a the end of the eighties by Sehuer, Wegner, al 11, 13}, who forthe fis tie prepared salable poly 2,3 aalky-1t-phenpine 6 eT, ips oak nat ny : a, pounds coating ary! mageesivm halide an aryl halide fonctions catalyzed by NiO) compounds. Herein, the subors stched tolbiliing side-chains at Ue 2. and 5- postions oF she beene ings and in order wo make soluble product, They Yiededoligc(maraphenylene)s with maximum degrees of poyieization of 10. The predicts are characorzad by an encive Iv linking of the benzene ‘ings of the main chain. However the molecular weights wer qe love ‘Several authors developed the meds fuer of HO} medises couplings to generate sever PPP derivatives (9. 13, 14. They described homocoupings of Sariou | -dilobenzene derivatives by means of tickeI)chleridftaphenyipho- sthinelte o he mekelOveyclceteenn comps 'Ni(Q)nedted homocoupings of 2-sutwiuted 14-phenylenebistiaes have teen repute by Ronee of ule {5] prove alata poy pepe 7 containing alkyh aryl oe eer subtitvents inthe 2- und 3 poss of the [henyrene skekion. Ths metned of prepruon appear 10 be bro! in Soop, expecially due to the eae of preparation of the DUE) mnorers saris Irom the conesponding hydrauinene derivatives cron omaen, MM {et - at sme COOte ‘By means of a repetitive Suzuki ryan cress coupling method, developed by Sehller, Weener ans co-workers the symiesis of solubilized PPP 6 with ‘tically increasad molecular weight number average up to 10D 14-phenylene {nit eae ponible[12} 2,5 Diy! substiacd PPPS 6 wer: ineasincly staid ' prottypes of so-called “hiry-r0d" macromelccuks, compened of nat, sigh PPP mnsin-hain and eable, “halt” alkyl sidechains. The indivi, shape per ssent macromolecules can be imaged By tamiton electron metescopy within ‘monolayers {16} Ply(2,3-die-deaeey-1f-phenylen) 6 (R: Cyl) reve ndwel-iype siete wk yer of phate sie-chsine pepondicular aad layers of dhe PPP mai chain parle to the sutra surface, Poly25-dh rok422 Oligo an Plyphnyens ‘yH1Aphenylene) of My 73000-94000 show a single anlsuoptc gud ental fine mesoptase in the molten state snd macromolecules with M, 44000-73000 ‘ive coentng iotopiclansoropic pases [17]. ~s- = Sis ati stow In altion to ally subst derivatives, soluble PPPs 6 ace aso known to- iy coal sony groups well x fone ie groups (cabony and wlonie ‘ct fonctions) [18], Schltr et i. roently deserted the generation of soluble PPPs deceete with densely packed senelly demanding dendnns on ie forme tien ofeylinticlly shaped deniers, so-called cylinder dendomer 19} ‘Scher al. [20] reporcd the syness of he PPP divaive 83, whichis compos of chin cycoghuse subunits, by means of a Suali-ype yl an! cose coupling of the coresponding diberonic Sed and cbromo menomer. The Ionomer yah the cycle -O-C gHlqrO- fotos ca Be reseed ite the pure a tiomers by erparative high presse uid chromatography on chiral tionary bases, The pure enantiomers were used lo generate the corresponding sereoreg= [ac and Syniioetc PP derivatives and He. Horby, the tesa des tive Bb is of special infers ew ts main-chain cial character [20 ‘Unsubsinted PPP possesses 3 25° twist between adjacent phenylene us TIL Since the rcoverlancpemtes asa function of the cosine of the twist angle, ven at 23° thee i 2 fair amount of conjugative iteration remning. IF one fice tubaitvonts along the PPP backbone (eg af the 2- ad S-pealins a it 6, Pend 8). te solbity is dramatically enhanced, as discussed above, howeve, the rowel is Fedueed Twist angen of 0-80" ropored fr ally subst fs in 25-postions (22. Ths, for poly(2-Sdialhy-rphenylenes only ahi Eble optical sbxomtion can be detected i the wavelet fegion above 4 am, "The rele described ths far sketch the synthetic demands fr being able 10 prepare promesbie, stuclually defined PPIS, in which the x conjupstion ro al fly intct or is even incresed as compared to that of ie parcat PPP 1 ‘Stem ‘The hey sep in the realzation of Was prance s the preparation of 3 PPP in which ihe amma subinits can be ebtaned in a planar or cay sihily twisted conformation in spite ofthe reduction of substituents “One of the frst exams isthe above meatened work from Yoshino eal (7 concerning the synthests of pay(®2-dulkyluorene)s vir oxidative coupling of fuerene Senvties. Poly®)S-oaihyinuoreae) deratves have be ab yh ‘Soa a Ni-apd Paatalzed ryan homo: and eros-coupling eations Of si 22 Pobmen 4 es a Sind PPP Oe Scheme 28. {ably substiuia monomer @27-dtwomoMure: aad Naw 27 dior id ‘ervaives, espetively) [23,34], These weactns allow the syrbess of tt rally defined progets possessing high molecular weights of up t0 100000, Some tlewvative eg te 9.9 dhocy subaticd polyiuoene or well defined thermo tropic LC slates scan be aligned on rue subsraes. These layers sow a high topics c€eremron, bali bt amet an petclnincscenee 25). The next step al Yess reactors were canid cut by Yamamoto eta (261, “They coupled 2,7 dior 9, 10-dhiydopheranrene 10 give an ethane Dade polyphenylene) derivative” [pol lOditydophenantvene-27diyD] 3) by Afoy of fowevalntskicl comple, which were ised ether scichiometically 8 eigen (COD) o mete femal clxtmtemiclly in the reaction xine ‘Ava sult ofthe inslcien soliton of the ethan sbsinents ony the oli- {gamer fracion wih Mge10U0 & soluble, the palymene prodocts pectin ot Seam jolie powder The value of Hn fr te soluble facon of 9 about $360 om, -ap- = jap: Scheme 29.442 Olga Pasiphenenes Consequently, by combining the synthetic procedure of Yamamoto (26) with the intodoction of more extended solubilizing substiuets, advantageous results swe capone. actor, skype cinyGrophersierencs oF enya Pyrees offered thanseves as starting monomers for the preparation of soluble ‘sepa Is of ths ype, 2,-Dion0-49-aky-4.39, Oseraydony ons (10) represent suite string moncmors for the relia of thx spate Toute. These diluncionaliza teaydropyrere monomers were fist reepared by Mille ol rece n'a Yams eoupting [27] Reaction ofthe dibronide 10 wih Ni{COD), ia DMFholune gave « poly(49- ialkyl-459,10se4yropyeene2,7diyl) PTHP 11 as completly soluble, new ype of PPP devivave, i which each prof neighboring aromatic igs is doubly bred wit ethano linkages (27. The slubitzng alkyl substiuens appear ca the tebe a cal tt yas oes ang of Pn PTHP it penseses a vclavely high number averge folcelat weight, Up to -M,=43000, sich coresponds fo coupling of about 100 THE units “A funher advantage of PTHDP 11s that dstereoreric forms can be zener which ate exehsively composed ot cis or Huns configured, nuance biking blocks The sceochensstry ofthe subatients in = ahd Spon (cs, ‘mans swonglysnfluences the sold state packing behavior of HL re PTHP 11 possesses the longest wavelength absorption Zp of 385 nm, almost teenie it the value forthe polylaorenes 3 of Yoshino al (7 Thus, ne pendent cofinnations exist forthe corectnes of this “nep-ladder concep: the fweducten of solubilizing groaps combined wih simultaneous bridging OF the ‘bunts gutrantees an iecresed degre of eonjugtive interaction. Tn solution PTIIP 11 exhbis intense blve phecluminescence (PL) wi rela Lively small Stokes silt between absorption and emision Gnas aboorten: 85 ‘dg. emission: 425 nn). PTHP 1 can be used a active component in light mii" Godes (LED) based on organic polymers, elecirofumanescence (EL) ‘quantum yields of O.1-0.13% (single ayer construction ITOMPTHP LUCa) of blue-green LEDs were reported. Blue polymer-based LEDs representa atactive target as blo emiting LEDs baxd on inorganic remicondsclor materials are ot fly acessible AS a vcsl of tet band gap energy of 27-82 eV, PPP deeiva- {hes ae panieulry sutable as ble emer In contrast to low malceulsr mass materi, polymeric emiers posses the ‘vantage that thy can te easily werked sno transparent films with lw degree 22 Polymers 45 of scaring. In ada, tey show a higher moeptological stability compared ‘with thar of vapor-dopeited low molecular weigh compounds. ne Yop Cention OC ME Mp Hove Uae) UNED OVE 10 man ‘ize the mutual distortion of aijacen' main-chain pheaylene units isthe incr poration of the PPP-parent chromophore ito the network of a completely planar leer polymer The perfect Mattning of the conjugated meyiem by bing ll the suhunits should the lead to maxinum conjogaive interaction. As wih the [PTHE 11 systems, akyl- ce ahoxy sie-cisns should Wad fo solubilization of the polymer. The alization of his idea culminated in 1991 in dhe fist symhess ‘of sclble and conjugated ladder polymer of the PPPaype by Scher and Mil len (28). This PPP ladder polymer LPPP 12 was prepated accowdig 10 3 50 called classical rou, in wach an open-chai,s Stcha ustep sequence was deubted Yor a Toi tine, and inthe eights sy lvcnous routes were stengly favor ss preparative moe for lade polyenes In classical mltiscp roe the eibeal pot is 10 conduct the ri closire ‘quately tal regione tn ihe ayes of LEP, he pct Ply ther 13 se ly propre ia an aya! coupling rom an arate direst {60 Se a soma dromoketons ~ do age ig = hits 2 FScatyt The cyetization 10 stuctwally defined, soluble LPPP then thes place in 2 two-step sauotee, consisting of rection of the keto group fellow by sing co sure ofthe sceondary alcohel groups of 14 in Fidel Craftssype slkyaticn, The result ladder polymer LEP 12 pessescs 4 number sverage molecu weigh of 25000, which conesponds to the inompraion of 65 penlene unis No sirare defects eld be deleted using NMR spectroscopy, LPP 12 i46 2 Olgo- ant Pobpherlee characterized by unusual electronic and optical properties: the absorption max ‘mum undergoes # marked bathochromic shift as 2 consequence of planarization of {ie chromophore 108 Aga, ¥alue of e840 tm (se Fig. 21), depending seme what on the substituents "Rand -R’. In addition, the longest wavelength #-2* ab Sorption band pessesss an unusually sarp absorption sige at al indiation for the fully planarizd, geometieally fixed ladder srt “The photluminescence (in solution) of LPPP 12 is very itene and blue (Ga emission ca. 460 at). The Siokes Sift between absorption sd emission fs ‘extremely small (ca, 150 cma consequence of the goometic fixation of the ‘chromophore inthe ladder structure The FL quatum yi ae igh in compar son to those of many ether conjugated polymers; insolation values between 60 Sand 90% have been measured, inthe slid ate up to 40% (29. PPP 1, syahesiod by Ue ICE precursor soute, slows « PL gana yield OF only 49 (30), Thus, the next ep waste investigate te suitably this new type | ‘mattal for appletion as an active compneat in organic materia based LEDs Inia. this fet the suring result ht although ffaient LEDs ean be pe pred wth LPR, the color ofthe mison in te sold state (him) is nevertheless Yellow (PL and EL}. te addon to primary eminem of the LPP 12 cum ‘hore inthe blve region, the PL and EL specs extubt an addional and unruc- {ured toad emisien Dand in the Yellow” regan (ea 6 nm) [31 The yellow mission band evold be unequivocally characerved as aggrezas emission by vat- fous plezes of photophysical evilene [12-34] and the occurence of exci for ‘raion unguesticahty ruled ent EL experiments showed thatthe yellow-emiting LEDs prepared from LEPP 12 exhibit quite remarkable characterises (Single yer constuction TTOLPEP 120Cs; quantum efficiency: ca 1.0%, applied volage: 4-6 V [35). These figures are an the range of the Dest values desenbed haber tor polynene emer tn ‘Single layer arangement, for example, pobpare-phenylenevnylese) PPV and PPV derivatives, gure 2 Atari a petdeminocence sacs of LAPP A (ule chute, RencpeChdle Re Soh 22 Polymers 47 From the perpetive of the stntegies aimed at fabrication of efficient blue LEDs, the results outlined above regarding yellow LPPP light emitting dies ae, evenness, unaisacoy. Ih onder 1a prepare blue LEDs trom LPP ‘alerts accesary wo eflcenly mk out or apres the doit yellow Bugrepae emisien. Supine the aarp onion i pol two ge eet ways ‘AL it the aggregate emassion coud be almost completly shut out by simply luting the LPP 12 with « matrix polymer. LEDs with 1% LPP 12 in ply(9- vinyleubazole) PVK as emiter muteril ae ctarsctrzed by a pure Hue hgh emission wih a quantum effiiency of ca 0.15% in singleajer configuration (TONE LUPP 12 in PVKICS) 135, 1 suppression ofthe aggregate emission i this fint example was based on pptely pysical principle, chemical modheaion ofthe LPP £2 structure vars the same aim iy aso possible. Ths, one option i the intedction of edition b> stituents nto the LPPP skeleton. Ataching an addtional methyl group the my lene belo of LPPP 12, bichon nde, sy be achoved by quanta Aspens, defined eligomers. The oligomers can be Bil p in & stepwise fshion, eg. be adden of epanometlic species wo cyclohexane rane flowed by momattation to the oligotarylene) (eg. for 25). ‘The alemative strategy involves the generation of oligodiyere mixtures of several oligomers of diferent chun lengths, eg. DY coppereaalyasd couplings of ‘mono: and diithcry, followed bya chremstogrptie reoltion of the elie fers mxtucs ino the menedisperse components 24 of defined chain kgs 25 Olgomers 31 obese — oco2od — ododd «= this way, oligomers 24 upto dacdesiphenslene dvivative hve been isolated by prepruve tundaver chronograph, [Recoly Run ta 150] prescsed the synesis of constitutionally homoge ecu liglpnenylene) Mah wath 2-S.alkyt wabsitunt, lect the Sate ‘somatic fing, generated vr the cross coupling reaction according to Suzski. Thy are exclusively linked in prepositions and consul of 15 benzene ings. “All the above oligomers are chartered by the presence of soloing sky ‘ycups,resllng nan increased solebilty, However te electronic property of the magstem are disturbed by the muwal disbrion of the phesylene unit in ‘duced by the stbstivens- Compre othe peat PPP sysem with ts 23° twit beteca ajacent building block, the substituted derivatives dpy dst st ihe of 0-40", which minimizes tke conjugative iteration within Un conjgatad Buckbone. One posubiity to oveteone ths draback the substation cy at the terminal ings a pvfonned by Lith er (51. They generated ligotghenyl ves 27 wil tert butyl subsints tthe lnnital 3 and S-posons using &522 Oligo and Potyponenes oleigsiolo 010}0-0-5-0 ololo = Serer 220 Grignard coupling as the hey step. Howeves, longer oligo(phenylene)s 27 are nat avalble fllowing tis apprach, sine tbe compounds become alse insoluble ‘when reaching chain lenis of mee than 7 aromatic building blocks. Sehome 221 AAs desenbed lor the comesponding polymers, & powerful strategy to achieve Soluble oligomers with maximum conjugative ineractien is © ineoporate the PPP backbone into a step lade (r ladder, se Section 22) framework in comb ‘tion with the atlachmers of soluiliang side groups ono the bridging futon lies. Following this, it was posible to generate shor-chuin tetthydbopyrere ‘oligomers ou separation of polydspersc mixtures into their (monodisperse) nd vidual components 28 with the aid of preparative ge! permeation ehomatogrphy ia a mo-8 soy 23 oligomers 53 With such a serio ofeigomers 28 aisle, the convergence of etial prope tes with ineresing chain length ean be monitored and the conjugation length in the comegonding polymer PTHP 11 can be determined as comprising of about 10 monomer biking locks (ie, 20 aromatic ings) [53 “The above appears 10 spatiesiz oligomers re SlePWSE synthesis, chron Aogrpie wselion of ogadiaperse mixtures) have mee recently been comple Imened by repelive medular strategies Such coreeps involve the repetition rected protectionlcoupingdcprotesion sequancm ina convergen! proces. 10 Iinimize the numberof eatin steps necessiry 10 generate the extended oligo- fers Such 8 siuegy wn developed e.g. for linear pol(para-phenylenectyyl- hels PPEs by Toure ul 38), Using similar approach, Schltr eal. 35] de Senbod the syatheis of monodsperse olig(phenylene) rods 29 with op 10 16 Phonylene rings snd ith welldafired functional end preps The symbess is sed om cavergent (exponential) growth using the Suz reaction ste cou- aca Seneme 2:2542 Otge and Pobiphenenes pling step. The key principle rests upon the significantly Faster ccupling of iodoar- functions as compared wo the conesponding bromesrys i the sryFaryl cre ‘coupling reaction according 10 Suzuki. Accordingly, building Becks contining bth todo and bromo functions undergo the coupling wih an aylbermic cx pe Seretnly athe odo se, loving the ueracted. bromo side for wibenjnt L+1 excitations, and i forbidden according 0 the selection rule: the whale testy becomes concentmied in the second cid stale oniating fom te interaction beween the H—» Let snd Hol —+ transitions. ‘The energy sphiting cieulted Detween the two excited sas in ‘eines continually when going from 30 A down w 35 A, as ustratd in Figure 45. It should be nod tha, at shor distances, the splating isnot symmetric with ‘espet tothe optical transition calcula forthe lad stilbene meu. “The one-cktronsructure ofthe oficial dimer also reveals thatthe spliting of the HOMO and LUMO levels sre rot equal (031 eV and 0.16 eV at 4A, respec- tel). The explain the reason why the H Let and Hel L tagsitions hse Uilerent Cl weighs in he desenpticn of the second excited state at short interchain ‘stances The lack of elecron hole symmcty reflects eangen she sength of Ue ‘overiap between the levels, the smaler LUMO splting ea be rationalized by th feet tha thee are more nodal surfaces i the LUMO waveluntion than 1 the HOMO. Indocd, the overlap of the mula exbitals 6 ade up of the sum of many sonic overlaps with palit of LCAO eoeffients: Ue lager the number ‘fal wfc th hag te posal of caneclaion of tems, dete dhe igs ‘ofthe prac of eoeficiens By extrapolation in aon: dimenstonal ack of ile Sting chins the valence Dan can be expected 10 be wider that the conduction nd The present resus ar highly relevant with spect charge transport prone ai owe 4. Scandic renin oe eh af igh tin RS il den ay tre chawe mpt y OO so eyo “14 berchain erections — ST 45 a = aur 43 INDOSCt eed anon ny fh od 4 tl ano of aia ‘ne ama years mc co oa nT fl i {2h woman ye kd ade Nc he er te Ral 18h coe ‘mito he wm hei ac se ch pes et me ssp Se ties in the sid ste, ince they are Consistent withthe typical observation tat in ‘onjugest polymers holes art noe mile dan electron. ‘We now address the way the properties, cleulsled for highly symm con- formato, are acted by the size of the ineracting Unit TO do 50, we have built compleaes formed by 1wo PPV oligomers coming up 10 7 phenyene ings and separated by 4 and 6A, respectively. In gener, the tends prevaling or in ‘eractngstients hold woe forthe lange chins. However, two tain difrencs (© The cial data eum He regime Of weak and song iteration epends on chain length; this evolution agrees with eater theoretical studi ‘ic have shown that models based on the eipole-lpele approximates own when the iatecaia Ustance wm weaker than the sive ofthe intrcting uit {60-62} Increstingly, this erica distance strates srownd 14 A: ths val cn be rewonably wsccaicd 40 the average separation baween the ecco snd The hole the excite sate, i) te second ricin dterence is thatthe sping betwocn the two Ko ex- ited sates, calculate a3 given separation diane, ken o Use su cat |y wih chai Kngth as stwn in Fine 46, Note hat this evolution cons984 Gas Phase 1 Solid Sune volt ofthe Blecrnic and Opneal Properties ‘with the molecular exciton model which pris the spliting to be properionl {o the oscar strength (hence, to inerese wih chain length). "These Tsu c40| tae simply atonal lo pertain theory bythe fot ta () the normalized RALCAO coefiints decrease with the number of sts L (as LG) the rele ‘oot motrin elements snc consiute by» product of fo ect (i no portioal to L~); and (i) the dominant mati tems ave disgonal and their mi bers proporional L. Therefore, te sum of the domiaan ens deserbing the strength ofthe interaction is proportional to L-. Though redaed, the ampliude of the spliuing is expec to be significant for chains ving s size cotespond ing to the typical effective conjugation lengils encounter! io plymer samples, However, for polymers thr ean be ellcively described a an infite chai, sch as MEH-FP in tgnly dea a ones potyenytene (Os) the sping could ‘become extemely smal In such a case, the interaction would lead to a resi of the lowest epical tsnston, as suggested by recent ighlycomlated cael ons performed on, ineracing. polyenes (60). Accordingly, the ‘would not be quenched by the mechanism proposed for finie-sine systems. We Te ako 0 bear in mind Wat the sis and sping Useused above Become lager when increasing the number of ncighboring chains, as dscussed below. Figure 4 Evan of he NDOSC cake sling ten he et oop ee {Toston rly two PPV che to of se moa om) shee epg ele ag, ec vu pee 44 Iuerai neractions — 99) [AL this stage, we can draw Several ayportant ennehisions erating the abu ‘ion and emission properties ot cOfacial diners formed by Iwo ilenicl PPV tii U) te lowest symmetry allowed optical ianstion involves the second excited se (ors higher jing sate at Son tlercham distances as town in able 1 a 35 A) and is biuesuftad wa respect tothe isolated molecule. Stch a evolution ins been observed experimentally fer silbene molecules [61] a for tbe Con ‘gard! systems (65-67) should also be noted Ut the He sit enpected from ‘ur calculations could te masked by ational effets suck as conorntionl changes upon interaction; for instance, an increase in the planarity of the con ‘ged backbone curseteristic of gaviguid 10 solid live ussiton could result faved shift ofthe lowest epics! tnsiton; (Gi due to the absence of optical coupling bebwces the ground and the lowest ‘excited sts, inkrmoleculrineracons ae expected o song affect the lan foseence efficiency, homevet, sane mr ay aay tha I PME Since the amplitude of the inerehain effects decreases with increasing chain Tens 44.2. Photoluminescence Propertis of Highly Symmetrical Complexes {nthe previous dietsion, we have not considered the posible iaflunce ofthe lange elecinn phone eaxpling tha ha tdemark of conjugal sprees fori ance, the equiitium geomery im the lowest excted sate can dif signili- ‘only from that in the grouid state 20, 6, 6911 fe therlone of nef i ‘stg the rle played by relaxation cifec inthe lowest excited stat, sss Ing there i enough ine or them to occu ‘As expected tbe AMUCLoptinied geometry of cola dimer formed by two largely seprited silbene molecules indicates tat one chain possess the typical pround tue geometry of un toad uit while te cae sal penis a equilibrium geometry characteristic of 3 single stilbene molecule in is lowest ‘excited ste. When the inechain distance is lowered, the Laie deformations ‘ain bighly asymmetric; this is usted im Table 42 where we have elect the C-C tend lenis i two sine Unis a various separation distances ‘Bien though tho chin, which ie inally in the ground-aate geometry, becomes ‘creasingly affected by the intermolecular itrstons wen te chin separation sexes, the major relaxation phenomena always lke place over a single can. The mostly intachain ckaracer ofthe exciton, alo suggested by ther thetic Stuties (70, 71, can be underscod 3s dhiven by the Coulomb aration between the eleckon and the Hoke. which ix mei ton she tuo shang sure ae ‘On the sane chain. Since ere an equal pebelty OF Finding the rled exc {on on each ofthe two chats ts wort sessing tha the most gra olan should be desctibad beyond the Boe Oppenheimer approximation a hncat combination OF the sxyonmetne Ses ye) $3) aD yyy tR)1004 Gas Phase w Sol Sate Esluton ofthe Electronic and Opel Papert a ee eee ‘peurincal puomets fr wl cl ar ea te igh a coi, O~© Th cs as 1 ta re Re 1306 15 ts me i Gn nm i te i ts 12 a 135 tse a he(Ro whore we have expicily noel thatthe equim gromety ofthe two Milecleshdiftercet However, when the dict i pot ina condemed phase it fcr scien shifts of he two sas can oecur and The eomect description ected 0 bey and yo and not (v2 w/ V2) 17 "The seltloclization of the clecvonrhole pit is eho supported by a detailed analysis of the wavefunction of the Kowes excited state Of a colcal dimer fermed by to fivering PPV oligomer. In analogy 10 what we have previous), sented, we have compuied the probably amplitude Ty ra 16, chain I of Trading te elecron on given Si, when Maing the Rok Ons 16 dh i {eof chain | ofthe dimer (ce Fig 7) ‘The corespondig wavefunction repre Sens « Gassian lineshape catered on the positon ofthe ole The probability of Tt the eacwon om chun ls. soning om intra exon ly 67% when the wo oligomers are separated by & A. Ths probability evolves ex Fonenialy with the hneonolelr uae A going from 281% at 33 A down O6% al 45 A (set of fg. 47), We enptusia tha change wanscr excited Suc ae observed at higher ene, the lowsst of the being O88 eV above the lowest exci sae forthe Iwo chains separ by 4A. tn thse ste, there isa lage probably of finding the electron on chai Ht when the bole sf on Er HOVSvver Be oy fa tortillas... * valli i. ‘ge 47, INDOISC aati of Gt gt x! wasn cil ine S01 ptr = dan epee Spang ented cig lanes on pak ‘Sanh the ue tng hscpcced fe pp Tes eve ahaha ey sac no ek Te above resus ince that the selection gues ae relaied when the goo lay modifieations taking place upon photecxcstion ae comidered Alou the {tanstion dipole moment between the ground sate and the lest exci it re1024 Gas Phase wo Sold Sta Evolution of the Electronic and OpicalPrpeties “lil oo ARERR an gan ste eae $8 SC am fe cs ot = 16 a of teri ec Ss nel cg aa su sie me tte w clon te Wut cacs Lhe ce Lacing Benne at epaed lectins andi ied with respect othe emion ofthe ingle molec. ‘Tass ihosraed Fg 49 whee we have pred ie INDOSC stew) {sonon and parece’ specs of 2 cola dime formato a fene lnc cara by 2 ge dates and by 4 A i pin of og ‘Sas th sath ht ear en ne the rahi of the eminton pk. The opal couping Breen to em pacers ekg ee eee ee = ike wavefunctions become incresingy spe for chain sepa. The ‘ait andthe atenaton ofthe eaten ipl peed Hy oor cals tore be lly conn acm exponen! erent pine he {Shiecence profs of PPV chs tn of ex Spy pe Site mrt oro of ncn etn 44 Inerhale erctione 108 \ wari Fee 49. INDOSCIsilie sto and enim spc of iene nok wi Seer ‘acl ie mc ye sic The main conclusion of this section is that interchain eoplings have not neces sarily to be associated to a subsanial decrease in the limiseacence quanteen Yield. As a mater of Fact, a Jewcane in tbe dive day Tle meee ve inporance of multiple non-aiaive decay routes. In cons the eftecave ‘sso of these channels can be greatly limited By the coninemest Of tke exctoes due 10, for exaple, the formation of exci to the migration of tbe vin gznened species towards regions whcte the chains ae srongly imerng Ge, the low-energy demain ofthe samples), as suggested by vcene permet sea ies (30.311 The actual luminescence thos raul fom the bala Of tese soe butions. In this conten, the significant increase inthe tative lice of Iminescence observed in recent studies [28,73] can be abut to the jot tla ‘axe of @ confinement proces and of the weak optical coupling batwoes the round sate and the lowest excite! se 44.3, The Influence of the Number and Relative Orientations (of the Interacting Molecules ‘The next sip in our study is go w bxyond the move comsdriion of two mole= ‘ues io a highly symmetie conigustion and to aes the changes tceurng a he calculated optical properties when inerossing the nantes of coc ea and when modulating the relative eicttions ofthe Chaim, tn ths come we have first investguc the props of one-dancisknal slacks conning eSHO! 4 Gar Paseo Sal Ste Broan ofthe Elin sant Optical Propet stilbene molecules at various separations. For lage interchain distances, we ob- ‘ecvathat a later contiting writ ives isc to a apting ofthe lowest exe Cited state of the isolated molecule intom nor-degeneat sates. Ths leas to the formation ofan excion band for an tite aay of unis a elegantly discussed bby Kasha (58, 59], The ene osllatr sensi is concentrated in the transition ‘between the giound state and the highest excited slate ofthe bind, ts leading © an hypsoctwomie shift ofthe lowest symmetry-llowed optical trasition, In con rst, the lowest exited state is not optically coupled to the ground site (= fount previously forthe coral mer) and 8 re-sfed wih espect to ei fle molecule. The width of the exciton band increases with the number of inte acting units but tends to samwate vapid this evoltion follows the way simple Hike calculations would describe the formation of bande i terns of tract for intrcsin anser integrals. ‘The sane picture also prevails inthe regime of ‘rong, interactions eacept atin some tsar several highlying ence tte. ‘ae calculated 10 be optically eoupled to the ground sie Regarding the emission properties, AMUCI calcitic, perform on 4 clas- {er containing the slbenemsolecucs separated by 4 A saw atthe rit tice deformations take place onthe central unit in the lowest excite Sse. I is therefore resonable o tun tht the wavefunction ef the land elcton hole pair extends at most over thos inersting cms. The raul urbe demonstrate thatthe weak coupling ulated between the ground sate and the owen ent ‘aie evolves in vay very simirto that reported for colacial diners. In ower to ass the posible inflacnee of posivonal disorder, we have cho- se 0 analyze the way Bisic operations such a8 tansatons se rotons alfect the properties calculsed for highly symametrc cnfigurions. This proach could [Provide guideline 1 prevent the hs uf aint spt euling Gewese ‘ground state andthe lowest excited sate, and hence the quenching of luniney ‘ence inthe sok se, ‘We start from a citer fomed by two oF thee imeracsing siltene amis see ‘ated by 4A, Sina uanslations of any unt alorg the cain ais or in diction Atansvere tothe chain axis (ee Fig. 410) i avery ieliclen process to recover 4 sinificant optical coupling. Referring to the dipole ince agprosimation, this ‘oplatned by the Mat that the elsive onetaions of the trnsiton ipo to ‘ments (which are polarized along the chin ais are not changed, tn al ease the Towest optical uation is weakly coupled 10 the ground site and the energy spliting beticen the lowest two excited atten i dhcly related 10 the werap ‘Denveen the wavefuntions of the two Unis ‘The second st of operauons involves raaing the mlecues, Stag fom & cofacial dimer consisting of two stilbene units sepsrated by 4 A, one molecu was rotated: (i) in the stacking plane around an ans perpendicular othe male Tar planes and passing through the center of dhe vitylene linkage; and i) ound is Tong axis, thos breaking the parallelism Between the molecular planes. Inthe later ow, the ealeulted prpertin are very similar to thovesbtined forthe oe facial diner beewse the relative oncattions of the tanston dipole moments rc Sill noc modiid. Inthe frst case, we observe that mereasng the age Beweeh | the chun axes ads w reduction of the spliting Between the lowest excited Shee fe tion pl col dtm by 0 ie meat G'S woman fore sn hath dnc ye tan a a oe ihe natn ofc sites te ag oe ats, duct a decree in ova fice. In adion a gnu the second eat site me lowe oom crane ar e 411 In such conformations stent fk cha to mies lininecens qancing te su sae The ae aa SR wo sce s ath an ah el ir cotaons re coir fr inane pao sineaal macs a sun, over lrg ange of tc dnance tie mo fete apcia ‘hoiogenrtl in the oes exe aa srs omy ei eae 3 ios hoy whan cnn chic The cause see hoe bron, ed tas neh eho (eatepeing he a106 4 Gas Phase 1 Soli Sue Exot ofthe Elect ad Opal Properties connor amen © zi ‘ ’ 1 und ee ste Sanestcnegnersaaares cos remanence ee re eee Sana seneeeee ese ane 45 Claes of Sexshiont Molecles 107 (00 on chin i Contr action wih «wepave polaron onan atc chain) a be generated in charge trasfereacted sss. The later ar found at enero, ‘gher than of he lowest nichin-eacied wae Since the average sop between the electro and te hole ia pola pairs not expected be igtiicanly itfrent from that in an intrachain exciton, the polation efiecs should nat Strongly stile the enengy ofthe charge wale enced sats wah agen tan ofthe lowest excited sate. The formation of polaron pair, observed in cea ox, evict suds 173), thus appears wo have an exits ovigin ince tread to the presence of impuries giving rise wo iterscions between chain of ifereat ‘ature and Iading wa reversal inthe ordering of inrachain vers intachein eer {ations Further thers and oxperonanil ties nae deta) ‘kestand the parameters governing the occurence of change anderen tafe be ‘ween itracting chins in more del In actual samples, the decay in unison i intimately connected w the concentation of itachi excitons wie eo

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