The Porphyrin Handbook Volume 6 / Applications: Past, Present and Future Editors Karl M. Kadish Department of Chemistry University of Houston Houston, Texas Kevin M. Smith Department of Chemistry University of California, Davis Davis, California Roger Guilard Faculté des Sciences Gabriel Université de Bourgogne Dijon, France a) ACADEMIC PRESS Aarau company SAN DIEGO SAN FRANCISCO NEW YORK BOSTON LONDON SYDNEY ToKYoApplications of Porphyrins 41 and Metalloporphyrins to Materials Chemistry JUN-HONG CHOU, * MARGARET E. KOSAL,* HARI SINGH NALWA,° NEAL A. RAKOW® and KENNETH S. SUSLICK* ® School of Chemical Sciences, University of Ilinols at Urbana-Champaign, Urbana, Ilincis 61801 USA ® Hitachi Research Laboratory, Hitachi Lt, Hitachi City barak, 319 1292 japan |. Introduction “4 Il, Photonic Materials : “4 ‘A. Mesogenic Porphyrns and Metalloporphyrins 44 1. Octa-Subsituted Porphyrin « fprbo sees oo “4 2. Teteasubstituted Porphyrin. Hodes deco a6 3. Disubstituted Porphytins .. +... ot 4 50 8. Porphysins and Metalloporphyrins as Nonlinear Optical Mates... --s.scsessee apepa 53 1, Second-Order NLO Systems ceeee cee boone pesseeeseee 54 2, Third-Order NLO Systems. : Benoonpabp oopbea al 3. Optical Limiting Systems : ceeee 61 C. Porphyrins and Metalloporphyrins as Opto- Materials. we 1. Artificial Photosymttetic Systems... eee a : 3 2. Porphyrins for Optoelectronics... oS 65 3. Synthetic Light-Harvesting Antennae. : ea . . 7 IIL Porphayrinie Solids... : cette R A. Microporous Solids 5 o : see 2 1. Porous Molecular Porphyrin Structures Boao oo 3 2. Hydrogen-Bonded Network Materials : 5 77 3. Metal-lon Coordination Network Wiatera's. 85 4, Porphyrin-Incorporated Zeolites : sevens 87 5. Clays and Layered Materials Incorporating Porphyrins 94 B. Conductive Polymers and Ferroelectrics. . 102 1, Conductive Porphyrin Polymers : seve - 102 2, Ferroelectric Porphyrin Materials... - mW . Porphytin-Based Chemical Sensars - . 4 1. Gas Sensors : an . m4 2. Sensors for Solution Species ‘i 120 WV. Conclusions 12 References : 128 he Parphyn Handbook Copy © 2000 by Academic He KM. Kai KML Sint RC AN ight of aprecucin in any form reenee Nolume 6/ Appetit: Pat Present and Folie TPS SN 01 2:383200.9/53000 4aChou etal. |. Introduction Porpliyrins and related macrocycles provide an extremely versatile synthetic base for a variety of materials applica- tions. The exploration of metalloporphytin assemblies as building blocks for tailored materials properties has gro%n rapidly during the past decade.’ In this chapter, we shall review the rather diverse applications of porphyrins to materials chemistry and try to draw the common threads between these topics, Porphyrins and metalloporphyrins have broad applica tions as field-esponsive materials, particularly for opto- clectronic applications. For example, the facile substitution ‘of the periphery of various porphyrins has generated a series ‘of unosual liquid crystalline materials, The porphyria ligand serves as a platform on which one can erect desirable molecular and materials properties, including very large dipole moments, polarizabilities, and hyperpotarizablities. The nonlinear optical properties of these materials are of special interest, in part for energy transfer with molecular control, and in part for potential applications in optical communications, data storage, and electrooptical signal processing. The stability of mono- and di-cation porphyrin ‘radicals makes these systems especially interesting. for photoionization processes, closely related to the so-called special-pair reaction center of photosynthesis and the photogeneration of electron transfer. Also, various poly- rmeric porphyrins have been examined for their unusual ow- dimensional conductivity. In contrast to their interaction with applied electric, amagaetic of electromagnetic fields, porphyrins and metal~ loporphiyrins can also interact with other chemical species. One might view such interactions a: chemo-responsive rather than field-esponsive. The development of chemo- responsive materials based on porphyrins, however, is somewhat less advanced. One example of such applications is that porphyrin solids, being highly porous, are involved in the current development of molecularly based molecular sieves or shape-selective solid catalysts. Porphyrins and metalloporphyrins have also been exarained for a variety of sensor applications, further proving their importance as a ‘lass of chemo-responsive materials. I. Photonic Materials ‘A. MESOGENIC PORPHYRINS Appendiing Tong alkyl chains to the periphery of a rigid tetrapyrrolic core has proved to be a general methodology for the synthesis of liquid crystalline materials, Liquid caystals possess yyoperties of both the liquid and solid phases, possessing order over intermediate distances, but retaining many of the theological properties of liquids. Phihalocyanine derivatives have been Widely investigated as thermotropic mesogenic: materials,** whereas porphyrins and metalloporphyrins have received only cursory examina- tion, The larger phthalocyanines tend to have high melting points; porphyrins offer a similar geometrical structure and a greater ease of functionalization, but have a smaller inner ccore and therefore lower, more useable melting points. The majority of porphytin mesogenic materials have a discotic ‘columnar nature in which the porphyrins stack like sauvers along their short axis, 1. Octa-substituted Porphyrins ‘The frst reported porphyrin exhibiting mesophasic behavior was an octa-p-substituted wro-porphyrin I octa-n-dodecyl ester (Figure 1) The investigation was modeled on the ‘observation that similarly shaped flat, hexagonal molecules had previously displayed discotic liquid crystal phases. Upon. heating, the porphyrin compound melted divecty fom a crystal to an isotropic liguid. During cooling, a meso- morphic phase of 0.1 °C was noted between 96.8 °C and 96.7 °C. This phase was characterized as having discotic ‘order via microscopic texture analysis and miscibility experiments in comparison to known discotic materials. Fox and coworkers have synthesized and investigated the physical properties of a series of octyl ether and octyl ester porphyrin materials. The ffee-base and motalated desiva- tives of 2,3,7,8, 12, 13,17, 18-actaks(f-n-alkoxy)ethyl- orpiytin, H((OCHap .JOEP) (abbreviations given in Table 1), were examined as possible liquid crystalline porphyrin materials (Figure 1). Of the frec-base species examined, only the n-octyl pocphyrin displayed a narrow five-degree liquid-crystaline phase (Table 2). The metalated (M=Zn, Cu, Pd, Ca) porphyrins demonstrated discotic metomorphism. The lowest melting point (61 °C) was observed for an equimolar mixture of the n-octyl and n-decyl zine octaether porphyrin materials. Appendage of a single electron donating cyano group to the 5-position of octyl octaether porphyrin [H,(OC.Hs 1X OECNP)] restlied in depression of the melting point and the clearing point. Substitution of an electron-tecepting nitro group in the same position [H3(OC,Han + .MOENO.P)] produced a depression of the clearing point without affecting. the ‘melting transition, chereby reducing the total range of Tiquid-erystalline behavior. The authors attibute this to distortion ofthe planar macrocyclic ring by the large nitro group.’ The free-base and zinc(II) derivatives of three similar octaester porphyrins (H;((O;C,Hap.)OEP)] were found to exhibit discotie columnar mesophases (Figure 2). Figure 1. Structure of uro-porphyrin | octa:n-dodecyt ester (ECH.CO;C Has, M—Hs) and other celyiether and ‘octylester porphyrins (R=CHjOC Han. 1,4, 6,8, 10 oF Ret CH2OsGyHan 4,6, 8 MH, Zn, Cu, PO, Ca.Table 1, Abbreviations 41 [Porphyrin Materials Chemistry 45 (DEYPD, 5,10,15,20-Diethylnylporphyrin polymer (OC. OEP (OCH! noEP (Coil JeyDPP (Giitany JCOHPP (OCH: ).Pa} DER (OCH sPHADFP ROC Hon + )PO],DPP. [OCH )PB]OHPP APTES: BICsHy«\O)y TP BDEY. Boy TPP DADPPYA D-a dabeo Den DEWM. ang berap b. bpp psc FISH EPR GIA Gl a Gre ERS 170 (MeyoEP)*? Mvit NLO OEP, OEPK oprap PBDCI TGSCo.pPr TGSCORIPP ‘1G'5-DaPP TO's-GIPP T3"5-G2pp Trt PP TaernC Fh PP Teen PP NC pHsO)etP ‘To-NHDPP Mo-OCHsCO.C HRP TipBOPP Tp-ChPP. Typ-cuyrr. ‘Kp-COSPP 3.17, [8-ootais (f-alkylesereylporpbyrinate IkoxyphenyDporpiyrinate 13,17 l-oetaks( ealkeoxy)ethy-S-cysnoporphytinate 13117, 18-oetakis(Bmalonythyl-S-niteoporphyrinate 2(3718.12,13.17,18-oetais(P-n alkoxy ethylporpytinate 5,15-ist-nalkyiyelohexy-d-sterpheny?porhyrinate ‘5.@-nallyleyctohexy!-t-eserpheny)-15--hydroxyphenyDposphyrinate 5,15 biG" akoxyphenyl-4-esterphenyl)porphyrinale 5:18-bist246-alkoxyphenyl-t-esterpheny)poephyrinate 5,15 bist'n-alkoxypienyl-4exterphenyDporpiysinte (8 -alkonypheny-esterphenyl)-15-(hydronyphenyporphyrinste 3-aminapropylrethoxalane 5,15-bi8634,9"4-etrealkony-o-terpheny! porphyrinste boron-dipyrin| Bipysidine 23,7.8,12.13,1718-octabromo-5 10,15,20tetraphenylporphyrinate 54 Gettin heyyy 814 ntophe} Hey 1020pheny phy jonor-accepior pair 14 Diazabseytooctane 15,20-deahyinyporphyrinate degenerate four-wave mixing Dimethyigyoximaio 5,10,15,20-teeaks((dimethyDtetrabenze)porphysinate diporphyrinate 5 20-ipheny porn ditferentiat scanning calorimetry electri Held induced second harmonic genceation electron pair resonance 3.54 tere buylphenylamido)benzoyt '-bis[3-5-dierebuty)phenylester benzoyl ‘31S bis "3 -bis(",5"-er?butyl)phenyleste)phenylesterIbenz0yl 24] permeation chomatography fhyper-Raplegh searing indlume-tin-oxide NINN" N"-euramethyl-octaethylporphyrin( +2) redhylvilogen dontinear optical 23,78 12,13,17,lSoctaethylporphyriate 2378121317 17-actaethy 18 oxe-porphyrinate ketone olyimethy! methacrylate) 5,18,10.20-bis(2,2"-[33-(p-phenylene)-dimethoxy}lipenyl}porphyrinate Feverse saturahle absorption Second harmonic generator conning tuneling microscope anion of suceinis acid $5,10,15,20-teuakis? 6-oci.G1A-phenyporphysinate 5;10,15,20-cetakis(26-hydroxyphenyporphysinate 5110.15.20 terakis3 siearboxyphenyl)perpsyrinate $,10,1520-tewakis3,S-dcarboxyatks phony poxphysinate 5110.15 20.0etaks(3,5-hydroxyphenyDporphyrinate 510,15/20-teteaki(2 6-Ota-G1-phenglporpyinate 51015,20-etrakis(26-oca-G2 phenyD)porplyrinate 5110,15,20-etrakis(4-n-dadeeylpheny! porpiyenate ncylphenyl)pophyrinate des ylpteny))porphyinate 10,15,20-tetakisG.4,3" 4 tetradodecyloxy-o-erpheny!)porphysinale 10,15 20-etrakis2-zmanophens) porphyinate 10)1520-tevatis@2-OCH,CO,C.H phenyl porphynate 10,15,20-erakis(d-bromophenyl)pergtiyrinate £.105,20-tetrakis(4-chlorophenyl)porpyrinate 5,10,1820-tetra-eyanophenyDporphyrinate 5110,15,20-teta(d-carbox) pheoylporphyinsteChou et al. Table 1 (continued) 5,10,15,20-Diethylnylporphysin polymer (DeyP, Tip RPP 5:10,15,20-eraks(4-uoropheny)porphyrinate TipNOPe 5110,15/20-teraks(4-niuopheny)parphyrinate Tprn-0collape? 5:10,15,20-tieakis(4-n-deeyloxyphenolporphyrinate Tipm0C PP 5110,15,20-erakis(4-n-dodecylaxyphenol)porphyrinate ‘TpOC PP 5:10,15/20-ttraks(¢-methaxyphens!)porphyrinate ‘Tp-ORNPP 510, 15/20-«ea(4hydroxyphenyl)porpyrinate ‘TCEMPP. (10,15 20-teurakis(4-carboethoxymethyleneoxy)phenylporphyrinate TENE tetacyanoethylene aePTRP 5,10, 15,20-tettakis(3-Muoropheny?\etrabenzoporphyrinate ‘TEreP 23,4 S-ietakist fuoroyetrabenzoporphyrinate 1, slats eanition temperate the twzahydrofuran THO. thi harmonic generation ‘TMA 510,18.20 cetra(S-imetylaminopentyDporphysinate TMAPTBP 10,15 20etrakis-dimethylaminopheny!etrabenzoparphyrinate ‘TMOPTRP 15, 20-etrakis4methoxyphenyltetrabenzoperphyenate Twp. 15,20-etrmetylporphyrnate ‘TwpTsP 15,20-etakinip-methviphenyDtetsbenzoporpbytinate ‘TMPyP 10,15 20-etrakis(&N-methypyridinium)porphyrinate ‘TMTEP 15, 20-tetramethytesabenzoporphysinate TPN 15,20-teraphenylaapithacene we 15,20-etaphenylporphyrinate ‘Terme 20.(etaphenylteteber2oporphyrinate ‘TeyP 20 tra: para pyridylporprinate The n-hexy ester exhibited lower melting points than either the n-butyl orn-oetyl species (Table 2).° Tt was noted that in both. the octaether and octaester porphyrin materials, rotallation contributed a stabilizing factor inducing wider ‘mesomorphic temperature regimes. The orienation of n-nonoxyethyl octa-substituted liquid- . Pe Figure 20, structure of catenane-substtuted di-phenyl pomphysin systems (Y = He m= 10, m= 0: orY = Hn 12, mT; Y= OCysHos: 0 =12, m ~ 2) Reprinted with permission from Wang, QM Brace, DW. Angew. Cher. Int Fd. Engl. 1997, 36,150, sn Figure 21, structure of catenane-substituted d-phenyl porphyrin systems with lateral chains (Y= Hm =I; or Y= OCH. 'm =2). Reprinted with permission from Wang, Q. M.; Bruce, D. W. ‘Angew. Chem. lt. Ed Engl. 1997, 36,150. Figure 22. structure of 515-683 phenyDporphyrin derivatives (R Free 0s oe CyHs0, Re Figure 23. Structure of 5,15-bis(3,4-didodecyloxypheny!) porphin Figure 24. Structure of 5,15-bis-idodecylonybipheny) porphyrin tion of one of the dodecyloxyl chains on each porphyrin with a proton generated a material with two discotic Jamellar mesophases. The clearing point of this compound (228.6 °C) was approximately 100° higher than that of either di-substituted compounds (136.7 and 132.9 °C, respectively).!* ‘Two other di-substituted species were examined by Ohta and coworkers. The tetra alkoxyl-containing 5,15-bis(3.4- didodecyloxyphenyporphyrin displayed a discotic lamel- Jar mesophase with a melting point of 60.4 °C and clearing point of 200.7 °C (Figure 23). Four erystalline phases and ‘one undetermined mesophase were delineated for 5,15- bis(4-didodecyloxybipheny))porphyrin between intial erys- tulline phase transitions at 40.1 °C to melting to the ‘esomorphie material at 430.9 °C (Figure 24) The material ‘was observed to decompose at 450.5 °C." B. PORPHYRINS AND METALLOPORPHYRINS ‘AS NONLINEAR OPTICAL MATERIALS ‘The synthesis and chemistry of nonlinear optical (NLO) porphyrin-based materials has been examined in some detail. Porphyrins have several desirable properties for use in optoelectronics: they have greater thermal stability (compared to typical organic chromophores); thes extended ‘-conjugated macrocyclic ring gives large NLO effects and subile variation in their physical properties can be made easily through chemical modification of their periphery Here we highlight progress in the development of NLO porphyrinic materials describing their second- and third- 335a Chou etal order nonlinear optical properties. Due to space limitations, wwe provide hete only the most cursory introduction (0 the physics of nonlinear optical phenomena; several excellent references are available for further detals.""” ‘The optical properties of a medium are characterized by the optical susceptibility, z. This parameter is closely selated to the refeactive index and the dielectric constant. In an ‘isotropic medium at optical frequencies («the relationship between the linear susceptibility, the refractive index (n), and the dielectric constant (2) can be expressed as: 1L4Any(e) = malo) = oo) o ‘The microscopic polarization (p) induced in an isolated molecule under the applied electric field (E) of an incident electromagnetic wave can be expressed by the following equation: pa aB+ PEE 2 Where p and E are related t0 the teasar quantities 1, By 7, which are referred to as the polarizability, first hyperpolar- ‘ability and second hyperpolarizability, respectively. Simi larly, the macroscopic polarization induced in the bulk media can also be expanded in the external field power pa OB + 28) BE +70 BEB + « where x ie is the linear optical susceptibility, and 7 and © are the second- and third-order nonlinear optical Susceptiblities; these physical meanings similar to their ‘microscopic counterparts, f, and, respectively. The even- onder tensor x is zero in a centrosymmettic environment, whereas the odd-order tensor z© does not have any symmetry restrictions and produces a nonvanishing higher-order optical susceptibility. Therefore, ° are (n+ 1) rank tensor associated with the nonlinear optical response of the medium, Both the field E and the polarization p are vectors, while the nonlinear optical Coefficients are tensors, The 7° is frequency dependent, and as a result, resonant and nonresonant parameters can differ significantly depending upon frequencies used. There are 9 clements of x", 27 elements of 7°), and 81 elements of 7; the number of independent elements, however, is usually much smaller, For example, in liquids, gasses and isouopic solids, there are only three = npn elements for x: 2? xen ayy and 2° Penns X 1. Second-Order NLO Systems Sustick er al™ measured the first hyperpolarizabiities (() of porphyrins having eleetron-donor (amino) and -acceptor (aitto) groups in the para-position of 5,10,15,20-substituted tetraphenylporphyrins (Figure 25) using ‘electric field induced second harmonic generation (EFISt) technique at 1.19 jm with chloroform solutions. The dipole moment (1) and ff values were affected by the position of donor and acceptor groups. A fl value of 30% 10~*" esu and dipole moment of 7», 10" esu,were measured for the porphytin having R! =R?=NOp, R= R'=NHb; and the porphyrin Figure 25, Structure of Sucks donor-acceptor “push-pull” tetraphenylporphytin, R=NO3 oF NH. with R!=NOp, R? = R = R* = NH exhiited « f value of 20 x 10- eu and dipole moment of 5 x 10"! esu Gay = 148176 x 10° esu = 1.64877 x 10-* Cm’). in these cases, the amino group “pushes” election density into the macroeycle while the nitro groups “pull,” increasing the hyperpolarizability substantially. The {value of a porphyzin with R' = R? = R! = NOs, Rt = NHfp was found to be 210 10" esu, The wellaligned charge transfer gives nse to large i values. Since second-order NLO response occurs only in a noncentrosymmetric environment, the incorporation of porphirins ito polar (in the sense of poled or asymmetric) array is mandatory for most optoelectronic applications. The importance of the organizational structure is shown in Figure 26. Langmuir-Blodgett (LB) films are an extcemely effective means of providing the necessary asymmetric environment for good NLO response. Suslick and coworkers incorporated similar “push-pull” porphyrins derivatives inlo LB films in onder t0 evaluate bulk response of the material.” They found that good films could be created from these push-pull porphyrins simply by conjugating a ees, Prenytyenscass = Organic Crystals Figure 26. Efects of environment on second-order NLO behavior41 [Porphyrin Materials Chemistry Prete nn) ean Mac ren (nocd) Figure 27. Langmuit-lodget isotherms or amphiphile derivatives of push-pull” porphyrins. Jong chain fatty acid tothe free phenylamine functionalities. ‘The mean molecular area of these LB films depended stzongly on the number of alkyl chains, as shown in the LB. isotherms (Figure 27). The number of alkyl chains did not change the porphyrin orientation, but rather altered the packing density of the porphyrins. Sen et al.##*) measured f values of a series of donor- acceptor substituted fuoroarylporphyrins by using hyper- Rayleigh scattering (HRS) at 1064 nm (Table 4). The first hyperpolarizabilities are influenced by the nature and position of donor and acceptor groups. An increase in f values was observed when a f-pyrrole position of the TPP chromophores was substituted with an electron-accepting nitro group. The open-shell Cu(ll) (4°) porphyrins show larger values than do closed-shell Zn(Il) (d'®) porphyrins. The high observed f values in Zn) porphyrins are due t0 the large change in dipole moment upon excitation, The highest values were obtained for porphyrins having N,N-dimethylamino and nitro substitu- ents. ‘These porphyrins absorb at 532nm;_ two-photon resonance enhancement contributes to large values but the effect of metal d-clectrons is more pronounced, Priyadarshy etal calculated the frst hyperpolarizabil- ities of porphyrin-bridged donor-acceptor molecules using semi-empirical INDO/SCI-SOS method. ‘The chemical structures and calculated f values are shown in Table 5, The f values of 5-(4'-dimethylaminophenyDethyny))-15- (G-nitrophenyethynyl)-10,20-diphenylporphyrinatozin- cll) (D-Zn(DPP)-A} (4) calculated at $30 and 1064nm Were 8152 x 10% and 477 x 10~*¥em°/esu, respec- tively. From such calculations, it is clear that resonant cthancements of hyperpolarizabilities can be extremely important. This makes comparison between experiments difficult unless the wavelengths used are far removed from the intense porphyrin absorbence bands. The calculated jf value at 1907nm was 2548 x 10-“*em'esu. The first hyperpolarizabilites are one order of magnitude larger than clber porphyrin-bridged donor-acceptor molecules. The dimethylamino-donor-nitro-acceptor zine species was determined to have a i value four times greater than that of a similar compound lacking the nitro-acceptor substi- ‘went. This indicate that extended m-conjugation length and Table 4, Structure and Fist Hyperpolarizability of Sen's f-Pyrole Substituted "Push-Pull” Fluroanyiperphyrins sac F x y M Buns 10 esu) F H 2 1.90 Cale. 1.20) NiCHs H a 720 (Cale 320) F No; 2H 10.1 ale 460) NCH NO: 2H 54.0 (Cale. 32.0) F Hl za 280 NCH H Za 112 F No: 2a us N(CH: NOs 2 920 F iH c 590 NCH» a a 2 F No» G 196 NCH NO: co 18 P.C: Day BG Keisha, V1 Ply. Chem, 196,100, Sho, il. Chee Soe, Far Tar 1997, 98,48 strength of donor and acceptor groups significantly increase the 8 value. The B value varied slightly as a function of aryl group composition for a series of compounds with Phenylamine donors and nitrophenyl or nitrophenylethynyl- acceptor groups. LeCoers et al.‘ synthesized push-pull arylethynyl porphyrins and measured their values by hyper-Rayleigh scattering (HRS) in chloroform solutions. The donor— acceptor compound D-Zn(DPP)-A produced approximately frequency independent fi values: 5142. x 10” esu at 830nm and 4933. x 10~% esu at 1064nm. The copper analogue (D-Cu(DPP))-A) exhibited frequency -dependent values of 4374 x 10” *"esu at $30 nm and 1501 x 102° esu at 1064 nm. Significant shifts in molecular dipole moment were observed for the push-pull arylethynyl porphyrins by electroabsorption or Stark effect spectto- scopy. ‘The fi value of the zine porphyrin dimer D-Zn(DPP)-Zn(DPP)-A calculated at 1064nm was 742 x 10- cm*/esu (Figure 28). The calculated 4 value at 1907 nm was 3299 x 10~cm*fesu. The P value of D-Za(DPP)-Zn(DPP)-A is. 1.6 times larger than that of D-Zn(DPP)-A. The larger fi value is associated with two Zo(DPP) units linked together by an ethynyl_bridge connecting the chromophores at their 5- and 5'positions ‘The first nickel push-pull 5,15-diphenylporphyrin derivatives were recently synthesized by Yeung. Using an amino arylethynyl group as the donor substituent and a formyl or a dicyanoethynyl group as the ucceptor group on 5556 Chou etal Table 5. INDO/SCLSOS Calculated f Values at 1064 am for Porphyrin-Bridged Donor-Acceptor Molecules Chon Ome memo, Na. Porphyrins ® Re ® Rt M (10 esu) 1 ZaDPP) Ph W Ph H Zn = 2 D-Zn(DPP) Bh D Ph H Zs 1067 3 ZnDUP)-A Py H Ph A 2s 1375 4 Dezupriya Ph D Ph A zm ans 5 Ph a Ph a i 509) 6 a 4 a a He 95.3 7 4 é 4 a ih 536 5 4 a a a rs 652 Source: Pjadaity, $3 These MJ Bertan, DN. Are Chae Se. 196,118 1508 ‘Figure 28. structure of LeCoer's zine porphyrin dimer. the porphyrin, the nickel-containing species exhibited significant first hyperpolarizability. Using EFISH at 1907 um, the rst hyperpolarizabilities were determined as 124 x 10” esu and 66 x 10~” exw for the formyl and dicyanoethynyl species, respectively. The larger B value for dicyanoethynyl compound is attributed to its higher relative electronie acceptor strength Albert ef a.* calculated # values of push-pull porphy- tins sing semi-empirical INDO/S Hamiltonian and singles- only Cl (Table 6). The calculated optimized f values and chemical structures are therein. The value increased as the benzene ring was replaced by an electron-deficient moiety such a8 diazene or tetra-azine ot by an electron-rich ring. such as thiophene or pyrrole. The Pes and if increased by & factor of two by replacing the benzene rings atthe donor end by electron-donating pyrrole rings. A series of porphyrins with reduced dihedral twist of the phenyl rings were synthesized and present very large fi values. Small dihedral angles were observed forthe alkyne bridged (7°) and for the azo-bridged species (0.5). ‘A multifunctional polyimide consisting of a free-base forphyin and a NLO chromophore. Nde chin. as synthesized by Peng and associates (Figure 29)" Fh LLr——. charge-transfer properties observed in porphytin electron acceptors of photosynthetic processes. The polyimide exhibited a T, of 250°C, Absorption peaks at 510, $40 ‘ind 630 nm from the porpiyrin rings and at 458 nm from the NLO-chromophore were observed. This multifunctional Bolyimide system is photoconductive as well as SHG active. ‘The photoconductivity was determined to be 1.1 x 10~ ‘Sfem under an external field of 1500V/em at 690 Dm, The polymer film showed a NLO coefficient dyy of 110pra/Vat 1L0644um after corona poling. Interestingly, the NLO coefficient dss showed no decay at 90 and 150°C, and the dy of 80% was retained even at 170°C after 120 hours. ‘This porphyrin-containing polyimide displayed higher NLO coefficient as well as stability of second harmonic generation at high temperature. Additional photorefractive effects were observed inthe two-beam coupling experiment.41 / Porphyrin Materials Chemistry * under zero-field tical gain coefficient of 22.2em~ jon was noted Another new photorefractive polyimide (Figure 30) with fa main-chain zine porphyrin (=0.005) and a NLO- ‘chromophore side chain (n= 0.995) was reported by Peng et «al This porphyrin-containing fluorinated polyimide dis- played aT, of 228 °C and maintained thermal stability to 350°C. The photoconductivity was found to be electrified dependent. The SHG remained unchanged to 180°C. Lietal.® looked at the SHG properties of self-assembled monolayer thin films of —tetra-para-pyridylporphyrin [HACTPyP)] and some derivatives on fused quartz and silicon surfaces. By covalently bonding the TPyP molecules to an alkyl- or phenyl-siloxy group, the centrosymmettic ‘able 6. INDO/S Hamitonian and Singls-Only CI Calculated f Values fr Pyrrole- Substituted Tapheny! Porphyrin x x x No. x y z 2.(10- esu) (10 * esu) ia N ci 6402 37.76 1b N N 7898 1549.74 le cH cH 75355 90832 ta N cH 8768 94284 ie N N 8502 122298, it cH cH 4602 38.73 Ip N cH 59.44 108233 th N N 69.35 135237 it ca cH 8083 39.91 i N cr 19 792.33 ik N N 83.14 107133 Nit, x x yt x4 ps0 nd 4, ii Lot Xo, No. x y z P, (0%? esu) 1p (10~** esu) Pm cH 14675 26388 » ca 19356 54547 2 N 245.39 5992558 ‘Chou etal Table 6. (continued) ake Nee Dn oh a Y ‘No. D A x 7 = Bx 1G esuyr 1B, (10-*8 esuy oo cea on a is a 3 os Bi gumentiae on : > my f b x \ ’ NOs HaGe Obs Figure 29. Structure of Peng’s porptytin polyimide, nature of the porphyrin is nullified, The SHG response at $532nm was observed (Yanx"2 x 10~* esu) This relatively large value was attributed to a completely delocalized ar-electron system in the in the porphyrin monolayer. 2. Third-Order NLO Systems As with phthalocyanines, the third-order nonlinear optical susceptibility, ©, of porphyrins can be manipulated by chemical substitution. The third-order NLO properties of several fetraphenylporphyrin compounds were first reported by Meloney er al The 1° was measured by the degenerate four-wave mixing (DFWM).technique from ‘oluene solutions of free-base, zine and cobalt-containing ‘TPs, The effective x‘ values of these materials were esti- rated from the thermally induced refractive index changes. All porphyrin derivatives showed y- values onthe order of 10~" esu, Sakaguchi et al" also used DFWM for deter- ining the y° values of cobalt, nickel, zinc, copper and ‘oxovanadium complexes of 5,10,15,20-eiralis(#-n-penta- decylphenyl)porpiyrins, Ha(Ti4-nC;sHy,)PP).. The mea surements were made in a benzene solution with conce trations of 0.02-0,05%. The 7 values were found to be in the range of 10" esu, however, these values ar influenced by concentration, The Cu{T4-n-CisH,)PP] having a 0.05% ‘weight dissolved in benzene showed © of 1.8 x 10" esu whereas the Ni(T(4-n-CisHs))PP] accorded x) of 107" su at a concentration of 0.5 8/L. The ° values did sot exhibit any significant effect of the metal atom. Rao ef al measured 7° values of a series of metal containing tetrabenzoporphyrin derivatives in tetrahytiro- furan employing the DFWM technique at 532nm. ‘The chemical structires of these porphyrins and their abbre- viated names ate listed below (Figure 31, Table 1). These benzoporphyrins were substituted at the” $,10,15,20-posi- tions with a variety of functional groups such as. m- fluorophenyl, p-iethoxyphenyl and p-riethylphenyl. Values as high as 2.8 x 10-"esu for z° were observed for zinc 5,f0,15,20-tetrakis(p-dimethylaminophenyl)ietrabenzopor- phyrin, Ha(TMAPTBP). In particular, large 7°! values were recorded for benzoporphyrins containing electron donating 45,10,15,20-phenyl groups. Guha et al. evaluated imagin- ‘ary ‘and real pans of 7 for the zine tetraphenyl ‘benzoporphyrin species [Zn(TPTBP)] and the p-methoxy- phenyl substituted. version [Zn(TMOPTBP)] in THF by using picosecond and nanosecond laser pulses. ‘The Jmaginary parts of x and y (second hyperpolarizability)41 [Porphyrin Materials Chemistry {HOG SE MIO Se ot) 9 ty Figure 31. Structure of Rao’ tettabenzoporphytin derivatives Zn(TMAPTEP): M=Zn, XH, R= p-Cobi- IN(CHs)x| 2a(TMTBP): M=Zn, X=H, R=CHs: 2n(TFPTEP): M= Zn, X= H, R= moFCaHy: Zn(TMOPTBP): Mezn, X= H, R= ph. H and 8-CHy, R=; Zn(TPTBP): M= Zn, X X=R=H, e aAL 6 EY Figure 32. Structure of Hosoda’s extended porphyrin ring system, of these two porphyrins at $32nm were found to be five to ten times larger than the real parts measured at 1.064 jam. ‘The Zn(TMOPTBP) showed an imaginary x" of 9 x 10°" esu and y of 8.0 x 10~™ esu whereas a x of approximately 1.8 x 10~"? esu and y of 1.6 x 10°" esu ‘was observed for Zn(TPTBP) at a concentration of 0.46 g/L. s0-CgHy; 2(TMPTSP): M=Zn, X=H, R= p-CHsCe j Mg(OMTBP):M— Mg, X-=8- H.R Gyhes 2nGTFTOP): MaZh, XP, R=: TOP: Nig, Nonlinear refractive index values (n;) of 7.8 x 10~"° and 9.1 x 10” cm?/MW were estimated for Zn(TMOPTBP) and Zn(IPTBP), respectively Hosada et al. measured 1° of spin-coated films of free-base and manganese-chloride derivatives of octacthyl- porphyrin (OEP) and N,N’.N".N’"-tetramethyl-octacthy!- porphyrin(+2) bis(trifluoroacetate) [Me (OEP) *)]_ by third harmonic generation (THG) at 1.907 jim to investigate the effect of increasing ring size on third-order optical nonlinearity (Figure 32). The x°° of Me}(OEP)~*, with an extended r-conjugation, was about five times larger than that of Ha(OEP), illustrating the increase in > as the number of m-electrons in the conjugated ring increases. A similar effect is observed in one-dimensional x-conjugated polymers such as polyacetylenes. Mn(OEP)CI showed slightly larger z° than Ha(OEP) presumably due to the inclusion of a metal atom. 5960 Chou etal . wD OO Figure 33. Structure of Norwoad's magnesium actaphenyl- tetazaporphysn. Figure 34. structure of Anderson’ 5,10,15,20-diethynylporptyrina- tozine polymer. fis cat Potynen) Figure 35. Structure of B30's porphyrin monomer and polymer, ‘Norwood and Sounik®S measured y° values of magne- sium octaphenyltctrazaporphyrin (Mg(OPTAP)) (Figure 33) as a 5% weight incorporation in poly(methyl methacrylate) (PMMA). The thin films showed Yer!” aNd Yayyx" values. of the order of 1.17107" and 3.03 x 10°" esu, respectively from DFWM at 598 nm, The ratio of Zxguy"” to oon was three, implying thatthe optical nonlinearity is, predominantly electronic. The Mg(OPTAP) showed a response time of 44 ps. Anderson et al synthesized the soluble conjugated porphyrin polymer of 5,10,15,20-diethylnyl zine porphyrin (DEIyP), using Glaser—Hay coupling (Figure 34). The real and imaginary components of 7° (~<0,0, 4) of these poly. mers were calculated from the elecroabsorption spectra. The (0940, 0,00) on the order of 7.310 "esu was obtain- Cal a the peak resonance due te resonance enhancement. Bao and Yu™ synthesize free-base and Zn-metallopor- phyrin-containing polymers Figure 35) and measured their 1.0 values by DEWM technique at $32 nm, These polymers, possess photaconductive and photovoltaic properties. Nota- Bie z" values were obtained for the polymeric materials. ‘The 7 value found for Za{TPP) was tice as large as the free-base porphyrin, The z°? values were on the order of 10°" eau for thin films. Polymer solutions showed 2° values of 1x 107! and 1.9% 10"? esa for the Ze and free-base porphysin polymer materials, respectively, which was more than two ordets of magnitude smaller than those ‘obtained for thin films. These z values were enbanced due (the resonant contributions. Kandasamy ef al®® measured sccond hyperpolarizahil- ites of six ttraphenylpomphytin derivatives using the scam technique at 784 um, The value grew with inere negative value of the Hammett constant. All porphyrins shovied negative » values both in neutal and acidic media. ‘The y value of porphyrins increased three to five times in an acidic medium compared to neutral. One species, Ha[T(o- OCH,CO,CHL)PP}, showed y values of =273.5 x 16-" esu in acidic medium, about 5 times larger chan in the neutral medium. The Ha[T(0-OCH,CO.C;H,)PP) material also accorded a 7 value 36 times farger than H,(TPP) in an acidic medium. The NLO properties of 1s{T(0-OCH- CO,CoH.)PP] were significantly higher than the other materials because of the substituted election donor groups a the ortho phenyl postions Kandasamy ef af* measured second hyperpolatizabil- itis of divalent MCIPP) detivatives using the Z-scan technique at 802 nm. The y value was enhanced by metal substitution, and i¢ increased from the completely filed <-shell of Zn to the partially filled d-shel of Cu and Ni. The ‘y value of Ni(TPP) was more than three times that of Figure 36, Structure of kumar’ basket handle porphytins (CuK XH CuCPSBK): RY =Br, REORE =H X= Br, CPi} Ro Br, Rn R= R7=ROH, X=). Reprinted with permission fram Peng, Z; Gharavi A Yu, L Polym, Pep 1995, 36,412n(TPP). The y value of Sn(1V) substituted 5,10,15,20- tctrakis(4-carboethoxymethyleneoxy)phenl] — porphytins [Sa(TCEMPP)X.; X=I", Ns , Br, Cl” or OH} was, determined by the same ‘method at’ 802nm in order t investigate the effect of axial ligand substitution on » values, ‘The y value inereased when a strongly electronegative axial ligand such as iodine was substituted, The high charge density at the core gives rise to larger y values. The large 7 value observed for the azido axial-ligand porphyrin originates from its strong electron-donor activity, ‘These porphyrins produced negative y values confirming their self= Gefocusing optical nontinearity. ‘Kumar et al.” reported third-onler optical nonlinearities in basket handle porphyrins (PSP using DFWM technique at 532m, (Figure 36). The planar CucTPP) porphyrin showed 2 (~ @;.0. ~ 0) of 1.03 x 107" esu, while the value for the rufffed PST molecules was found to be approximately 10" esu, ‘The x° of thin flms of Cop andl HeCTPP) composites ‘were measured by a research team at Naval Research Laboratory using DFWM and nonlinear transmission at 590.5 nm.9%61 Kajzar and associates‘ measured 7° values 41 [Porphyrin Materials Chemistry in multilayer and composite C-based thin films with tclraphenylporphyrin, Ha(TPP), and. tetraphenylnaphtha- cone, H,(TPN), using THG at 1.907 win, Lower 7 values were observed for both composite films and multilayered structures compared to Cp films. ‘Thisd-order nonlinearity of solution-state and thin films of triethoxysilane-substitated Zn(TPP)_ polymers, were examined by Sinha et al! Using, DEWM, 7° was measured in solution at 3.06 10~" esu at $32nm and 0.36 x 107" esu at 1064 nim, demonstrating resonance enhancement at the higher frequency. A cured polysiloxane film containing the same porphyrin provided a x of 3.25 10" esu at 532nm. The corresponding 7 values were determined to be 2449 x 10~"? and 2.81 x 107" tsu, in solution at $32 and 1064nm, respectively, and 60.10 x 10 esu for the thin film at 532 nm. Additionally, the polymer film was determined to be thermally stable in excess of 500 °C by thermogravimetric analysis ‘A comparison of the third-order optical nonlinearity on various metalloporphyrins results is. summarized below (Table 7). The 7° values vary as much as seven onders of ‘magnitude depending upon chemical structures, measure- “able 7, Tird-Order Nonlinear Optical Susceptibility Data of Metalloporphyrins Compounds Measured by Different Techniques Poxphyrin 210" esu) x9) 0-" es) Wavelength (un) Measurement technique Reference HTP) — 286 oss Dewn 0 -i02 = 0802 Zen 38 ‘zat = aa 032 DRWM 50 ~ 166 = 0802 ZSean 38 ‘cote = 716 0332 DEWM 50 HaICusPP) = 400 oss DEWM I Coltidn-Ctts PPI = 560 0382 DEWM 31 NiMGn-Cyals PP] 0 0332 DEWM 31 Culten-C PP) = 500 an DEWM 3 af Ta-C HPP = 150 0332 DEWM 31 VET a-C cif PPI) — 320 0532 DEWM 31 ZNTMAPTBE) wo 28000 0332 DEWM 3 ‘ZaCrarBP) 33 (000 0332 DEWM 32 ZacrFPTRP) 38 1300 0332 DEWM 2 2acrMOPTBP) a 14,000 0332 DEWM. 2 ‘0010 0078 Toes OKE, 3 ZacTMPTBP) 40 12.000 0532 Dew 2 Maou?) 16 8000 0532 DEWM 3 Za TPTBP) 090 3000 0532 DEWM. 2 ‘0.0018 091 05e OK 33 2acre TBP) 070 2000) 0582 DEWM 2 sucteP) 050 3000 0332 DEWM 3 Hopp ioose 19 1307 HG 4 Mn(OEPIC) 6.006 26 Loan THG 3 Meo)? 0028 10 1907 THG 34 MglOPTAP) 117 0598 DeWM 35 Porphyrin potymee = 73,000 = = 36 EDEN monomer = 06 0532 Dawn u ‘Zu(DEEyP) monomer = 12 0582 5 DELP), pol 310 0532 5 (zaDE9 I polymer = a8 0532 37 arp a = 0784 253 apy 482 = 0788 253 crys ~ 65 = O74 253 TPP} 67 = 0784 253 (reps =63 = 0.784 353 amps = 62 = O74 233 CacteDy 267 = 0802 ss Nic, a5n8 = oxo 58 SOCTCEMPP 097 = 0802 3862 Chou et al. Table 7. (continued) Porphyria yO es) 10 es) Wavelength (um) Measurement technique Reference SaCICEMPPIND: = 802 ZSean 3 SHTCEMBE Br. = 0802 Zein 5s Sw PCEMEP)CI = oso? ZScan 58 SacTCEMFP)(OI» = 0x02 Zean ss cust) 038 033 Drews 3 CPS 050 os DEW, 39 Cursti) 087 oss DaWM 8 ‘CUPSIBE) 080 8332 DIWM 8 Cumsicl) 035 DEWM 0 acre) 103 DEWnt 2 CeosHBR) (iid = DEWM. «0 eo TP) rtayer) a THC, eo egTPP) (composite) ns HG 2 Soutes: Nala, B.S. ln Nonlinear Optics f Organic Molecular and Polymeric roll, igure 37. Structure of Sh’s metallotexapnyin compounds (= Cd, RH, G, CH; M = Sn, R= HM = Ga, Figure 38. Structure of u's PoctabromeCtPe}s(M = Hy, Co, Cu, Pb, ca, 2), ment technique, wavelength, state of matter and resonant contributions. 3. Optical Limiting Systems Optical limiting properties of fullerenes, porphyrins and hhuman eye protection from high-intensity visible light sources 65 Although metallophthalocyanines have been stodied in etal, there are few reports on optical limiting properties of porphysins. Blau ef al showed reverse saturable absorp- tion (RSA) by cobalt and zine TPP complexes. Fei et a7 reported RSA in Fe(TPP). Nonlinear excited state absorp tion in a series of metallotexaphyrin compounds (Figure 37) “Matera, Navn, WS, Miya, S, Haas CRC Pre Boca Ratt, FL, 1997, {in acetonitrile solutions using 8 s and 23 ps optical pulses at 532mm Was noted by Shi et al. The texaphyrin com- pounds show reverse saturable absorption at weakly fluorescent bands for nanosecond pulses, while saturable absorption occurs for highly fluorescent bands only for picosecond pulses. A siv-level model was presented to explain the nonlinear absomption effects. Cadmium texa- phyrin showed strong RSA and nonlinear absorption whereas these properties were very weak in the other ‘metallotexaphyrin derivatives. ‘Su and Cooper" reported optical limiting properties of free-base octabromo-tetraphenylporphyrin H(BrgTPP) and its _metai-comaining derivatives (Figure 38). Nonlinear ‘optical absorption efficiency was measured at 532m. The efficiency data showed a trend as Zn(BrgTPP) > Ca(Bre ‘TPP)>HaBrsTPP)>PHIBRTPP) > Cu(Brs TPP) ® Cd-Bry- ‘TRP) which was related to the spin state of the central metal atont, Comparable to phthalocyanines, Zn(BrsTPP) showed the strongest nonlinear absorption ‘efficiency observed ‘among porphyrins, C. PORPHYRINS AND METALLOPORPHYRINS, ‘AS OPTO-MATERIALS JIn photosynthesis, the chlorophylls and pheophytins (close ‘cousins of metalloporphyrins and porphyrins, respectively) play key roles in adsorbing light energy over a wide spectral range and converting it into the highly directional transfer of| electrons.” Its a marvelous but highly complex process that has inspired considerable interest in the synthesis of porphyrin arrays. A biomimetic approach to the photosyn- thetic apparatus may also lead to applications of similar systems a§ optoelectronic devices. After brief overviews of artificial photosynthetic models and light-harvesting anten- nae to se the stage, this section will focus predominantly on porphyrinic materials in applications to optoelectronics. ‘The remarkable efficiency of reaction-center photocher istry has encouraged the design and the study of synthetic ‘models. Most research on artificial photosynthesis has been directed toward mimicry of the natural reaction center (RO): ‘The center functions as a molecular-scale solar photovoltaic device that converts light energy into chemical energy that ‘can be transported and stored for maintenance, growth, and41 [Porphyrin Materials Chemistry reproduction ofthe organism. Green plants employ chloro- phyll, magnesium-chlorn, as the chromophore to harvest light."The trapped light energy is used to promote electrons into higheneray excited states. However, these excited sates tend to decay to their ground states within nano- seconds, wasting the harvested energy 2 heat. Chromo- pphotes in green plants prevent this ftom happening. by extremely rapid electron transfer. The acceptors. an chlorophyll and pheophytin molecules initially, and qui nones eventually. The resulting separation of negative and positive charges atthe reaction center preserves 2 substan tial fraction of the photon energy as chemical potent nergy by generating a potential across the organelle membrane. At the minimum, then, an artificial action center requires some kind of chromophore that can absorb fight and act as an electron donor, an electron acceptor, and an organized superstructure that controls the electronic interaction between the donor andthe acceptor. Initial work con mode! systems involved simple mixing of donor pigment molecules with acceptor molecules in solution. ‘The electron-transfer events were monitored by observing ion pars that were the result of donorfacceptor collisions. Fash photolysis, nanosecond, and pico- second-emission spec- troscopy were used to characterize transient intermediates to beter understand electron transfer kinetics 1. Atti ial Photosynthetic Systems Achieving @ long-lived charge separation after photoin- duced electron transfer is the Key to realizing artificial photosynthesis. This section will focus on molecules designed to maximize the lifetime of « charge-separated state. The ultimate goal here isto create a sufficiently long- lived excited state so that chemical reactions can compete with the back reaction and convert the excitedstate free energy into a less volatile form. The frst such systems, developed in the 1970s, were molecules consisting of synthetic porphyrins covalently linked to quinones. ‘The porphycin fistexcited singlet state isa strong reductant and is easly observed by flash kinetics. Simple porphyrin— quinone complexes are relatively easy to synthesize, The use of porphyrin pairs (asin the reaction center itself) is a amore dificult challenge, however.” Following absorption of light, the porphyrin’ (P) transfers an electron to the quinone (Q) resulting charge-Separated state consisting of A cationic radical P"' and an anionic Q’~. The lifetime of P' —Q"~ is usually very short because of the back-reac- tion, The electron rapidly returns to the porphyrin molecule, losing energy as hat, and the ground state ofthe molecule is restored Kong and Loach described the first reaction-center mimic to have a covalently bound porphyrin—quinone linkage.”*” Shordy thereafter, Tabushi and coworkers designed a porphyrinquinone’ molecule iz which the uinone is bound to the porphyrin via an amide linkage." ‘These early systems outined the basic conditions on, which later systems cramatically improved. An extensive collee- tion of porphyrin—guinone model compounds have been ‘enerated forthe purpose of investigating long-lived charge- separated states. This overview will not be comprehensive, oO Figure 39. Gust and Moores tad (top) and pentad (bottom) and Wasielewsh's tad (mide. Reprint with Detmission from Moore, TA; Gust, D. Mathis, P-; Migiocg J.C; Chachaly,C. Bensasson, Vj Land, Eh Bos), 0.; Lacel, PA! Lehman, Fi; Nemeth, G.A; Moore, At. Nate 1984, 107,630 6864 but instead will discuss a few illustrative examples. Interested readers are encouraged to consult an excellent review by Wasielewski on this subject."! Substantial success has been made in using these complexes for biomimetic studies. In the 1980s, Gust and Moore showed that the back reaction could be slowed substantially using a “triad” molecule composed of a {etraphenylporphysin covalently linked to both a carotenoid and a quinone.*2-*® The slowing results from the formation ‘of the charge-separated state in which the two radical ions are separated by a neutral porphyrin (Figure 39). Carotenoid Porphiyrin-quinone molecules possess a long-lived ion- pair lifetime on the microsecond timescale, For comparison, 2 typical donor-acceptor excited state lives for only several hundred picoseconds duct efficient charge recombination, Wasielewski and coworkers designed an ctaethylporphyrin triad to affect a long-lived chargo- separated state also based on the multistep principles found Jn carotenoid systems, The donor and acceptor distance was controlled by triptycene-derived quinone ancl amine groups. Electron transfer from N, N-dimethylaniline (D) to P* was competitive with charge recombination in the D-P* -Q state; therefore, a long-lived charge-separated state was ‘observed. Gust and Moore incorporated the successful multi- step strategy in a pentad comprised of carotenoid-dipor- phyzin-diquinone subunits. The pentad adopted an extended Chou etal linear shape about 80A in length. Irradiation at 650nm produced the porphyrin firstexcited-singlet state, which Underwent series of complex electron-transfer”events The final charge-separated state D"?-P*~Q" was long lived and formed with a quantum yield that approached unity. Inthe early 1990s, Osuka developed elaborate covalently linked porphyrin dimers bound to @ quinone election scceptot, tethered via an aromatic hydrocarbon linkage." ‘The strictural and functional aspects found in reaction center chromophores were modeled using stacked porphr- ins that roughly mimic special pair, at feast in_ general structure (Figure 40), Because Osuka’s system featured octa-alkylated porphyrins asthe primary donor, the optically welldefined P’" cation intermediate absorption at 601m provided a suitable marker to monitor transients The anthracene-pillared coplanar system had charge- separated-state lifetimes that survived for only several hundred picosecands. One disadvantage to this system is the large separation between the porphyrin faces in the porphyrin pair relative to that found in the photosynthetic reaction-center special pair, ‘suka has also designed a system comprised of a zinc porphyrin dimer (DP), a zinc porphyrin monomer (ZnP), and & pyromellitimide (pm) in place of the quinone (Figure 41)" The pyrometitimide anion absorbs at Figure 40. Osuka's stacked porphyrin models for tho special pat.Figure 42. Molec iad of ciaryloorphyrn(P)carotenoid polyene (C)ullerene (Cs). Reprinted with perisson from Liddel,P, A; Kuclauskas, D.; Sumida, J.P; Nash, B.;Nouyen,D. Moore, AL; Mocre, TA Gust, 0. Am. Chem, Soe 1997, 119, 1400. is spectrally resolved from the porphyrin absorption bands. Upon photoexcitation in THE at $32 nm, these triads give DP ~ZnP-pm ion pairs with lifetime of 2.4 4s in relatively low quantum yield. By replacing the intermediate Zn porphyrin with the nonmetalated free base," reasonable functional similarity to the photosyn- thetic reaction center was obtained, An efficient electron- transfer relay, 'DP*-P-pm—DP*—-P-pm— DP -P- fam, was observed, similar to the primary electron-transfer events in the reaction centers ‘A spectacular example of a long-lived, charge-separated donor-acceptor triad was demonstrated by Gust and Moore." The Arizona researchers reported @ molecular triad consisting of a diarylporphyrin (P) covalently linked to a carotenoid polyene (C) and a fullerene (Co) (Figure 42). Jn 2-methyltetrahydrofuran solution, the ‘rad undergoes Photoinduced electron uansfer to” yield C-P"! -Cip, Which evolves into C"* -P-Cig_ with an overall quantum yield of 0.14. This state decays by charge recombination to Yield the carotenoid triplet state with a time constant of 170ns. The results demonstrate that fullerenes can act a effective primary electron acceptors in multicompo- nent systems that generate long-lived charge-separated states. The C”' ~PCp ~ charge-separated state recombines, to yield the carotenoid triplet state, rather than the molecular tOund state, as in photosyztheti reaction centers, Finally it should be mentioned that among the numerous synthetic analogues made for the photosynthetic reaction center," nearly all utilize a single porphyrin asthe inital photoelectron donor rather than utilize a porphyrinic dimer as in the reaction center. The use of face-to-face bisporphyrin complexes linked to a quinone is perhaps the 1most sophisticated of these analogues and provides a stat- ing point forcombination of synthetic light-harvesting systems ‘with synthetic electron donor-acceptor complexes.7792 2. Porphytins for Optoclectronics ‘A main goal of microelectronics is the design of electronic switches, wires, transistors and gates made of single molecules, Approaches to this goal borrow heavily from the photosynthetic reaction center, both in their physics and in their chemistry. In principle, porphyrin arrays connected with conducting or insulting’ molecular wires could be converted into such molecular photoelectronic devices. In practice, however, the majority of the models have yet 10 function as electronic switching devices or molecular wires. ‘Toward that goal, Wasielewski er al. have designed 2 molecule (Figure 43a) consisting of two porphyrin donors rigidly attached tothe two-electron acceptor NN . Reprinted with permission from ‘Wagner, F; Lindsey, J. 8. |. Am. Chem. Soc: 1994, 176, $758, © 1984 Aineican Chemical Socal. APD?) (Figure 436), in which they selectively excite the second donor, Zine S-phenyl-10,15,20-tri(n-penty))por- phyrin (D') and phenyldimethylpyrromethene dye (D*) ‘were chosen because they can be independently excited at 416 and 512mm, respectively. The two acceptors were chosen because their ground states absorb only weakly at 416 and 512 nm and their radical-anion absorption bands are well separated. 7Wo ultrafast (150 fs) laser pulses were ‘used to control the rate of & photoinduced electron transfer within the molecule. ‘The results suggest that this type of molecule may lead to the realization of molecular electronic devices.41 /Porphyin Materials Chemisty (au Hon y N Toe, SCO i N. Bu vt e = fe ry Bu Figure 45. Molecular vires prepared by Crossley and Burn, Reprinted with permission from Crossley, M.;Burn, Pel} Chem: Soc, Chem Commun, 1991, 1560, Lindsey and Wagner have investigated a variety of mult porphysin arrays that are connected by diarylethyne bridges for studies of artificial photosynthesis and molecular photonics. They have synthesized a “molecular photonic wire” consisting of an array of metalloporphyrins 90 A in length.” The difference between molecular electronic ‘wite and molecular photonic wire is thatthe latter supposts excited-state energy transfer rather than the electron hole- transfer process. This photonic wire consists of @ boron- ipyrromethene dye as an input chromophore at one end, @ linear array of three zinc porphyrins as a signal-transmission clement, and a free-base porphyrin as an optical output clement at the other end (Figure 44), Absorption of @ photon by the input chromophore at one end causes the emission of a photon as the optical output at the other end. ‘The overall yield of energy transmission from input 0 output is 76%. Crossley and Bum also reported @ molecular wire based on a more conjugated backbone.” The tetrakis(por phyrin) is about 65 in length and possesses a number of tert-butylporphyrin groups along the backbone that provide the molecule with good solubility in number ‘of organic solvent systems. Individual porphyrins are either dircetly fused or are linked by a copianar aromatic system and are expected to be reasonably conductive (Figure 45). ‘The synthesis ofthis extended pexphyrin system involved a seven-step procedure. The final porphyrin tetramer was ‘obtained by the condensation of porphyrin-a- (SbF (THF), and Ma!(TPP) (MeOH),(SbClg )-(CH2- CliH)z. The latter compound was also characterized as having multiple channels (Figure 62).!2° Channel width was genesally observed to be on the order of 3.4-6.0A, Some of the smallest guestfilled channels Were observed in the Zn(TPP)m-fiuoronitrobenzene)., Zn(TPPY(2.4-dinitrobenzene)» and Zn(TPPXacridine), sys- tems, all of which had channel widths calculated at less than 4A. The largest spacing for a “normal” clathrate material was observed for Ru’ TPP)[(PhoP)2Me]a(CH2CI,).'” B74 ‘Chou et a. Figure 52. Windmilsike porphyrin arrays, Reprinted wits permission from Nakano, A. Osuka, A; Yamazaki Yamazaki T; Nishimura, Y: Angew. Chem. nt. Ed Engl 1998, 37, 3023, Layered materials with d(002) spacing of 6.8A were ‘observed for Rh!"(TPP)(benzylisocyano)(PFs )2 in which a single layer of guest molecules is located between a double layer of the host porphyrin species, and an even larger d(002) spacing of 7.8 A was noted for a material with 1a double layer of host Ce™(TPP)*? separated by another double layer of phthalocyanine molecules and SbCle anions (Figure 63).""7 Pursued applications of these clathrate “porphyrin sponges” include their use as materials to selectively “immobilize and isolate molecular species” and as inter- calation compounds. ‘The forces holding these solids41 / Porphyrin Materials Chemistry Figure $3. Convergent stratogy forthe synthesis of porphyrin pentamer. Reprinted with pormission from Prathapen, 8; Johnson, T; Lindsey, J. Am. Chem, Soc. 1993, 115, 7519, 7576 aesea Figure 54, The synthetic routes of 4{BDPV benzaldehyde, 3,5-ie(BDPY}benzaldehye: o o Chou et al condensation reactions for PDPY-subsfiuted porphyrin arrays NaS ay: POPY41 [Porphyrin Materials Chemistry Figure 55. Se-ssembly of square multiporphysin arays. Reprinted with permission fom Oram, C. M,; Lehn, JM. . Chem. Soc, Chem, Commun. 1994, 2313. Together, however, ate very weak. Consequently, upon removal of solvent, rapid structural changes to a different crystalline phase or to an amorphous material typically ‘occur. In some cases, reintroduction of a vapor-phase guest to the desolvated materials can produce a powder pattem that matched that, of the crystalline clathrate materials ‘grown in solution.!%* One specific application mentioned incorporating insect altrctants as guest species into the lattice clathrate materals.'” Goldberg and coworkers have synthesized porphyrinic solids that utilize other weak intermolecular interactions between porphyrin building blocks. The structures of inclusion compounds formed from halogen-substituted tetraphenylporphyrins displayed three general motifs. The ‘most commonly dhserved patterns involve halogen-halogen attractions between the kelo-substituted phenyl groups and attractions between halogen atums and f/-pyrrole hydrogen atoms; these can lead to both one- and two-dimensional auays (Figure 64), Inclusion compounds of this variety were observed for ZalT(p-C)PP] species with guests: guaiacol, nitrobenzene, DMSO, methy! salicylate,"2? methyl pheny!- acetate, mesitylene, ethyl benzoate and acetophenone." and Zn{T(p-B1)PP] species with guests: benzylacetate, methyl salicylate, ethyl benzoate, bromobenzene or p-xylene.” The intermolecular Cl-++Cl distance defines the width of the guest cavities. The CI---Cl separation of 3.63A reported for ZalTip-CI)PP|-C7Hs0: (Figure 65) is typical of the 1:1 inclusion complexes; values for 1:2 inclusion compounds such as. Zn{Tp-CDPP]-2C:H,08 (G.9GA) wore higher”? Slightly offset stacking of the porphyrin macrocycles in subsequent layers defined the depth of the cavities. The intermolecular Br---Br contact distances were reported as 3.837A for a 1:2 ZnlT\p- By)PP]-2CsHs0s (methyl salicylate) inclusion material Thermal gravimetric analysis (TGA) was reported for ZolTip-BIPPI-2CgHOs, showing a 21% weight loss for {oss of solvent (theoretical 23%) at ~ 125°C without further loss to 350 °C." In the case of the 1:1 Zn(Tip- CH)PP[/nitroberizene inclusion compound, the observed helical arrangement of the porphyrin backbone produced a polarized cavity environment (Figure 66), Guest molecules were observed to order in response."”” The p-xylene clathrate of Zn{T(p-F)PP} featured a linear chain structure similar to that noted in the chloro- and romo-derivatives However, the nonbonding F:--F contact distances have increased to 4.1 and 4,2A, characteristic of a repuisive teraction rather than an attractive force as observed in other halogenated porphyrin materials." A second motif observed by Strouse and coworkers is characterized by tightly packed herringbone-like layers igure 67). Structures of this type were observed for ZalT(p-CDPP]-CsH;Cl__(o-chlorotoluene),"? —Zn{Tip- BO)PP|-ACSHSN and Zn[T(p-BOPP]-4C3H2__(mesity- lene)!" In the p-bromo compounds, ligation of two pyridines to the Zn(If) ion was observed, The remaining uncoordinated guest molecules were observed t0 occupy voids between the porphyrin moieties. ‘A third motif, also observed in Strouse’s TPP materials, is characterized by tightly packed corrugated layers in which the guest molecules intercalate between the layers: Za{Tip-BNPPL-ACeHLN (aniline) and Za[Tp-Bd)PP] 2CyHi,N (methylbenzylansine) Figure 68). 2. Hydrogen-Bonded Network Materials In an effort to synthesize more robust frameworks, hydrogen-bond interactions have been explored as basis for linking porphyrin molecules. Hydrogen bonds offer the additional advantages of divectionality and selectivity." While hydrogen bonding is certainly a stronger interaction than the van der Waals interactions that hold the “porphyrin sponge” solids together, even multiple hydrogen bonds per porphyrin still provide’ only modest stabilization of the solids in the absence oftheir solvates.Chou et al. cae Figure 56, A 21-component mulporphyrn array. Reprinted wth permission from Drain, C. M.; Lehn, ot. ‘Chem. Soe, Chem. Commun. 1994, 2313. Goldberg and coworkers have explored a number of substituted tetraphenylporphyrins as building blocks for porous solids. Some of the inclusion compounds of 5.10,15,20-tera(4-hydroxy)phenyl porphyrins Hal (p= (OH)PP| featured structures similar to those observed in Jislogenated species." In a motif similar to the previously observed linear polymeric chains, the Zn{T(p-OH)PP] -2- CH0-2H,0 (phenol), Zn{T(p-OH)PP]-2C3H 0 - Hz0 (benzyl acetate) and Zn(T(p-OH)PP] + 2C7H,0 + HO (ben- zaldehyide) clathrate materials are characterized by dual cis- side OH-OH_ intermolecular attractions. There are no intermolecular interactions between para-substituted hydro- xyl groups and f-pyzrole hydrogen stoms of adjacent linear chains (as observed in the halogenated materials). Instead, para-substituted. hydroxyl groups hydrogen bond with hydroxyl groups on adjacent linear chains, forming a two- dimensional porphyrin network. A guest’ water molecule participates in this interchain bonding arrangement (Figure 69), In this manner, two different guest cavities ae formed—voids between porphyrins ina polymeric chain and between chains in the two-dimensional array. Layers are stacked in an offset manner, therefore forming pores instead, of channels in which axially coordinated ligands partially ‘ecupy the voids in successive layers. ‘Similar cis-side OH.--- OH interactions are observed in the CulT(p-OH)PP]-4CsHsO (acetophenone), ZalYip- OFDPP|-2Cskhyg ACHLOH (e-xylene and methanol) and Za[T(p-OH)PP]-5C)HyO> (guaiacol) materials. The linear porphyrinic chains are separated by guest molecules wich hydrogen bond to the hydroxyl groups (Figure 70). In the acetophenone and o-xylene included materials, porphyrin macrocyclic planes of successive layers are offset prevent- ing the formation of distinct channels. ‘The parallel porphyrin macrocycles of successive layers are directly41 /Porphyrin Materials Chemistry Figure 57. Porphyrin arrays linked by yne and polyyne units Reprinted with permission from Ui, ¥ ; DIMagno, 8. Gy; Thelen, Mi]. Science 1994, 264, 1105. aligned inthe gusiacol-included material generating ~9 A cavities, "Sandwiched" between layers of porphyrin mmacrcycles isa single pralll-orientated guest molecule GEigure 71). There is another guest gusiacol molecule situated below the azea of hydrogen bonding between porphyrin molecules,!” Forthe toluene inclusion slid Za(T(p-OH)PP)-3CyHa, three-dimensional framework is observed (Figure 72). Hydrogen bonding between trans-orenated porphyrin hyronyl groups and parallel chains form a geometry approximating a body-centred cubic arrangement. Por pysins within successive layers of tan Chains have a interlayer separation of 6.5 Ain which a guest molecule resides. Channels perpendicular to the layers of Porphyrin chains are observed The sigtficattanslatonl and rotational disorder of guest species in the crystal sr ture supports the presence of channels. Trans-OH interactions. define the framework of the Zn[T(p-OH)- PP]-26,H,0-2H,0 (p-eresol) inclusion solid, One-dimen- sional hydrogen-bonded chains between trans-hydrorjl soups on porphyrins, which are sacked pany overlapping Figure 58. Porphyrin and guest packing in a typical porphyrin sponge, Reprinted with permission from Bytn, MPs Curtis © Hsiou, Ye Khan, . Sawin, PAs Tendlick, 5. Terzis, A; Stowe, C E J. Amer. Chem, Sac. 1993, 113, 9480. © 1993 American Chemical Society the porphyrin macrocyclic ring, results in a layered material ‘with intercalated guest species (Figure 73). ‘The clathrate of equimolar 5,10,15,20-tetra(4-methoxy)- phenylporphyrinatozinc({), phenol and water, Zn{T(p- OCHs)PP] -CeHcOH,0, exhibits intermolecular hydro- gen-bonding between methoxy substituents and axially ‘coordinated water molecules in successive porphyrin layers Figure 74), This arrangement generates a three-dimen- sional cross-linked framework in which phenol molecules ‘occupy cavities between layers of porphyrin molecules similar to results reported for tetraphenylporphyrin inclu- sion solids by Strouse with m-xylene guest molecules." A. corrugated sheet-like geometry is observed in the Zn[T(p- CHOH)PP]-2CHO, (o-hydroxyacetophenone) material (Figure 75). For clathrates of 5,10,15,20-tetra(¢-cyano)phenyl por- phyrin, H(T(p-CN)PP), four structural motifs were encoun- tered by Goldberg et ai." The first hydrogen-bonding motif involves open two-dimensional networks in which a cyano80 Chou etal. FRR HOR OR OR +2 (Piperidine)y Cd*? (1,4-Dioxane)2 wie FR WR GIG Fe +? (THF), Za*? (THF) asa ak adDqadD qd Co*? (Piperidine) Zn*? (1,5-Cyclooctadiene) WK RRR FOR HG Zn*2 (Trioxane)2 ig +? (Piperidine)> Figure 59. Examples of typical porphyrin sponges with 1:2 porphyrin: quest rato. Repented with permission from Bym, M.P.. uns, C.J; Khan, 8.1; Savin, PA; Tsurumy, R; Stouse, C.. Amer. Chem. Soc. 1990, 772, 1868. © 1990 American Chemical Soiay41 Porphyrin Mateos Chemisty a FRE PRR WO HOR Zn” Phenanthrene 2H* p-Xylene Eaure 6. Pooh sponges wih age guest moleoes Reps wth persion om Bn M. PCat Cod; Khan, 1; Sawin, P.A; Tsurumi, Sttouse, CE. Amer Chem. Soc. 1990, 712, 1865. © 1980 ‘American Chemical Society, Figure 61. Basie packing mot for porphyrin clatrates in 6, 5, and 4.coordnate TPP complexes. Reprinted wi permission ftom Byrn, MP; Curtis, C. .; Goleberg,L;siou, ¥; Knan, S.L; Sawin, P-A; Tendick, 8. K. ‘Skouse, C. EJ. Amer Chem, Soe, 1991, 173, 6549. © 1991 American Chemical Society82 Chou etal eee: Oy Ore "yg pet G fos Mn*4(MeOH)9(SbCl6>) Fe*(Urocanate’ (CoClgH)2 (THF) Figure 62. Examples of materia with high porphyrino-quost rigs. Reprinted! wth permission ftom Byrn, MIP; Curtis, C.J; Goldberg, 1; Hsiou,Y- Khan, . |, Sawin, P. A; Tendiek, SK, Sttouse, C.E,. Amer. Chem, Soe. 991, 113, 6549, © 1904 Amarcan Chemica! Socely BOR BER BOR Peet Fe"*(Benzylisocyano)(dibenzaminecarbene)(PF 5") eR He RR le ce Figure 63. Examples of aered lalate mati, Reptnled by pemison fom Bin, M. PCC J Fado than 1; Sain, PA Tene & Tos As Shouse, 6-6] Aer Ch os 198 173, 54000 1980 Aineccan Chemical Sosy.41 /Porphytin Materials Chemistry CliBr Figure 64, Schematic of interporphytn interactions in p-chioro- and p-bromo-subsituted TPP. Reprinted with permission from Dastidar,P.; Krupitsky, H; Stein, 2; Goldberg, | ncusion Phenom. Mol, Recognit. Chem 4996, 24, 24% group hydrogen bonds to f-hydrogen atoms on an adjacent Porphyrin pyrrole rings in a dimeric fashion (Figure 76). The individual [~C=N --- H-(-pyrole)] interactions sae described as short (3.61~3.59 A) and linear, although the two H-bond interactions ofthe dimer are not parallel to each other. The 1:2 inclusion compound of Cul T(p-CN)PP] with chloroform produced framework with elliptical interporphyrin cavities (6.4 x 11 A) (Figure 77) whereas larger square-shaped cavities (10. 10) were observed for Zn(Ti(p-CN)PP} with two ethyl benzoate molecules — one axially ligated to the central Znv(fl) ion and the other located within the inteporphyrin void (Figure 78) One-dimensional chains utilizing similar dimeric inter- actions were observed for the inclusion solids ZnlT(p- CN)PP]-3C)HyOp (Where the solvate is guaiacol) and ZalT(p-CN)PP]-2.5C)H,O (anisole) (Figure 79). In the usiacol-included material, a 20.06. x 4.1 A cavity is noted. A similar structure is observed for Zn{T(p-NO,)PP]- 3CioH1.02 (eugenol) with a large eavity of dimensions 23.34 4.19. (Figure 80). Herringbone-type interchain interaction between a single cyano substituent and a f- pyrrole hydrogen atom is characteristic of the third type of pattern observed for para-cyanophenyl porphyrin mate- rials (Figure 81), Interlayer spacing of 4.3 A was observed for ZalT(p-CN)PP] CHCh, + CH. In the Cu(TD porphyrin species, CulT(p-CN)PP] - 2CgHsNOo, cross-linking between adjacent chains is observed (Figure 82). The fourth bonding patter utilizes ligand-to-metal coordination and is addressed subsequentl.!*” Two clathrates of 5,10,15,20-tetra(4-carboxy)phenylpor- phyrin have been reported by Dasitidar ef al! Interpene- tating networks in the 1:1 Zn(TpCPP)/see-phenethyl alcohol included material are formed when a porphyrin ‘molecule hydrogen bonds to four other porphyrins via “typical” carboxylic acid dimer aggregation. A planar two- . Reprinted with permission trom Kumar, RK: Balasubramanian, 8; Goldberg |. Inorg. Chem. 1998, 37,41. © 1988 Gordon anc Breach Pushers, Figure 83. Interporphyrin bonding, layered structure and cavities in Zn(TACPP)-CsH.y0. Reprinted with petmssion from asta, P.; Sten, Z; Goldberg, l; Strouse, CE, Supramol. Chem, 1996, 7, 257. © Gordon find Breach Publishers +. Layered Double Hydroxides and Other Layered Materials Anionic porphyrins and metalloporphyrins can be ion exchanged into layered double hydroxide (LDH) materials (Figure 113), The first example of an LDH-porphyrin ‘composite material was reported by Kato and coworkers 1989.""" "The X-ray powder-diffraction pattem of the intercalated material showed the d-spacing increased to 224 from 8.0A upon intercalation. This increase in the 99100 ‘Chou etal Figure 84. Intrporphysn bonding and intorponetrating networks in 2n(TpCPP)-3C;HySO. Reprinted wit permission from Dasfiar,P.; Stein, Z; Goldberg, I; Strouse, C.E. Supramol. Chern. 1996, 7, 257. © Gordon Sd Breach Publishers “Table &. Channel Volumes for Various Porphyrin Completes Porphyrin Solvate Void “otal channel Unit cell yoltme/unit_volume/unit—volume/unit volume unit Porphyrin complex Z_volume (a) col) cell’) cell? A) cell? i) acter) 1 819 390.8 ° a1 211 (263%) BAIT" S-DHPIP]-5 BiOAC 11st e208 ans 960.2 (60.7%) HATO"¢-DHP)P]-4 BIOAC 2 m09 180 oo 15379 [555%] HAITA"S-DHPYP] +7 CaHsCN 2 Gan Inti 1587 25694 (67.4%) ZAITO"G-DUPPIEIOAC),-2 OAC 1 1387.2 a0 168, $832 [2.08] ZA(T3'5!-DHP)PICTEP) "3 CHCl "2 TH 1 assr6 7558 3269 5417 152.7%) Ma(T('-DHP)PICTHF)2 Cl 2 a89 16122 1Bss So THE CHC. Sorc: Bayappa, Pe Wilson, S Ry Suck, KS Amer Chem Son 997,19, 8492 = Delisle van der Wal oles were clclaad om Quan foreach oi ell. Void volume is Gefne ws he wi ll volume nas the sam of {he porphin value and te solvate solune: For the mealloporpyi, the somes of he cordinuts igands were counted a pac the porphyrin vome ‘a shanal value i deine hsm of wo an sate Yume, AS Vales techs ete portage offal chnt! sue ee ell 2616.7 (62.4%)41 / Porphyrin Materials Chemistry Figure 85. 5 10,15,20-Tetrakit?6- Ru> Fe) and the more z-acidie bridging ligand (e.g. pyz. > bpy > dabeo). The X-ray single crystal structure of the related nonmacrocyelic metal complex [Co!-(dmeH), (Py2)leo Confirmed that the polymeric shish kebab-type structure. can be formed with symmetric multiatom bridges."*° 4. Covalent, Conjugated Porphyrin Polymers Porphiyrins linked with conjugated organic bridges form another subclass of conductive porphyrin materials. Work toward such polymers was done by Crossley and coworkers, who synthesized linearly conjugated porphyrin systems." Figure 116 illustrates their conjugated tetrakis(porphytin) materials. Preliminary spectroscopic data on this system indicated significant decrease in the HOMO-LUMO gap (by about 08 eV) compared withthe porphyrin monomer. In related studies, Yo etal. used the Heck coupling reaction 19 synthesize conjugsted porphyrinie polymers.¥*" A series of polymers (Figure 117) were generated with M, values of 5,000 to 46,000. The polymers were soluble in’ range of organic solvents and were east as optical films onto glass slides. Their conductivities were studied, showing a steady increase in current upon photo irrediation, Recent studies by Tones and cowarkers have produced conjugated porphyrin polymers with oligophenyleneviny- lene bridges." Using the Wittig reaction, as illustrated in Figure 118, a series of polymers were synthesized and labeled PP1 through PPS, The molecular weighs, as determined by GPC, were inversely proportional to bridge length, ranging from M, = 6692 (PP3) to 12230 (PPI). To increase solubility of the polymers in organic solvents, long, Figure 100. Packing arrangement in [Cu(TPyP)-Cu]2* lramework, Larger cles ropresent copper ions. Solvent and noncoordinating anions omited for carly. Reprnted with permission fom Abrahams, B. Fi; Hoskins, B, F. Michal, D. M; Robson, R. Noture 1994, 369,727. © 1994 Me Milan Publishers Li.108)41 [Porphyrin Materials Chemistry 109) 30.00 Angstroms. Figure 102. Parallel polymeric porphyrin bands shoving coordinate bonding between letrabidentate porphysn ‘atboxyate and calcum ions botn as space-fling and schematic rogels (Cop. In his schematic model, Intersecton of oyinders represents tne centr ofthe porphyrin macrocyel and comers represent calcium fons. Extended three dimensional stucture showing Inlerpenetraon of porphyrin bands (bottor). Guest pyrisine ‘rolecules and coordinated water lenuias have bean omitted for cant. alkoxy groups were appended to the bridges, permitting conductivities to approximately 10~* Q~'em~'. The casting of porphyrin films from coluene solution. Prelimin- visible spectrum of the doped polymer, which showed red ary results showed that the nondoped polymers had shifting of the absorption bands relative to the porphyrin conductivities of less than 10°! Q~em~', Doping with monomer, was indicative of the nsrrowed HOMO-LUMO nitomethane solutions of anhydrous FeCl, increased gap.110 - Chou etal Figure 104. Crystal packing in Mai) coordinative network of Mal) derivative of Hs(TPCPP),41 /Porphyrin Materials Chemistry Figure 105. Crystal packing in Ho(DICarPP) molecuar species showing channe's between porphyrin columns. Solvent molecules omitted for cay ©. Conductive Porphyrin-Linked Polymers end Porphyrin Arrays ‘Another approach taken toward the creation of porphytin- containing conductive polymers has been to incorporate Porphyrins ints the backbone of traditional conductive polymers. This approach has been studied extensively by Shimidau and coworkers." As shown in Figure 119, PCTPP)Ct)2 can react with thieny] or oligothienyl alcohols, to generate the corresponding polymer precursors. Electro- chemical oxidation of the thiophene-containing precursor ives the polymer, These types of polymers have also been built two-dimensionally via electrochemical polymerization of 5,10,15,20-oligothienyl-substituted porphyrins. The I-D polymers are particularly interesting in that the conductivity is enhanced by photoirradiation, The conductivities of poly. 2 and poly-3 were 1.2 x 10~°Q~!em~! and 5.1 x 10° Q-'cm-1, respectively, under dark conditions. When irradiated with photons from &.500-W Xe lamp, conductiv- ity enhancements of greater than threefold were seen 2. Ferroelectric Porphyrin Materials Very little work has been done in the development of coordination polymers as molecular-based ferroelectric materials. Ferroelectrics carry a permanent, macroscopic electric dipole moment (i.¢., polarization) in the absence of an electric field. Furthermore, the polarization of ferro- electric materials can be switched with the application of an extemal electric field, Ferroelectrics have unusual electro- optical, photorefractive and pyroelectric properties. They can be Fabricated into electronic oscillators, high frequency filters, electroacoustic converters, pyroelectric radiant- energy receivers, and nonlinear capacitive elements. Most ferroelectrics are metal oxides!®2-! (such ag BaTiO; and LiNbO); a few are Yiquid-crystal materials.!9°-"® In a further development of the shish kebab class of polymers, metalloporphyrin-coordination polymers have ‘cen suggested as possible ferroelectric materials."*?"7° Coordination polymers of nonplanar metalloporphyrins with nonsymmetrical bridging ligands carry an aligned mm2 Chou et al Figure 106, Schematic ofzeolte L main channel (tp) and idenize6 2n(TPyP**) methyvologan (MV2*), ‘complex (bottom). Reprinted with permission from Persea, L. Bard, A.J. Canplon, A: Fox, M. A, Malou, TE; Webber, S., While, J. M.j. Amer Chem. Soc. 1987, 108, 7308. © 1987 American Chomical Society : oo 2| 7 g . | é < ol a ime ee : ee ge 0 te EymiV ve SCE Figure 107, Cyclic voltammograms obtained for CuTPPy/zelite ‘modified crborepaste electrode In absence (A, presence (8) of 15% 10" moll hyerazin and a 1.0% 10" Small Estee (C). Supporting eects of €.5malL" NaCiOg at HI and a Scan rate of 20 m3". Reprinted with permission from thy, C2} 0,56; Pang, Wa; Che, CM chem Commun. 1997, 65, dipole moment along the stacking axis (Figure 120). The dipole moment originates from the charge separation between the bowl-shaped porphyrinato core and the metal ‘tom (Figure 121). The metal atom tends to be pulled out of| the porphyrin plane by strong axial ligands. If the ‘metalloporphyrin has two different axial ligands, the metal atom will be pulled toward one side, depending on relative ligation strength and steric demands, Various monomeric structures of metalloporphyrins””* 2 suggest that a ouble-well potential can be present, as shown schemati- cally in Figure 122, By analogy to the metal oxide Woveleagtinm Figure 108, Difuse reflectance spectra of zeolite ¥ with encapsulated MACTMP) showing porphyrin Soret band (top) and Min fons bottam). Reprinted ith permission from Nakamura, M Tatu, Ts Tominaga, H. Bul Chem. Soc Jpr. 1980, 63, 3334, ccompounds,”"*-" the direction ofthe bulk polarization in such coordination polymers may respond to an external field Suslick and Chen have prepared several one-dimensional coordination polymers of metalloporphyrins with nonsym- metric bridging ligands (Figure 123) as candidates for molecular ferroelectric materials.4#%2° Metallopor- phycin complexes of Fe(Hl), Fe(iI) and Sn(1V) were examined, Structures determined by single-crystal X-ray diffraction include , (Fe! (TPP)(pyCN)}x., (Fel (TPP)- (PyCO.)].c, and [Fe™ (TPP)(ImPHO)].. (Figure 124). The chain alignment of the bridging ligand is disordered in [Fe"(TPP\(pyCN)]o, antiparallel in [Fe’" (TPP)(py- COp)]as, but aligned ‘and polar in [Fe'! (TPP\ImPhO)]..47 /Porphyrin Materials Chemistry 113, Figure 109. Compatson of dioxygen and argon absorption isotherms of GoctvP)/zeaite ¥ materia at 25°C. Reprinted wath permission from Ly, G. Qy Govind, R Inorg. Chin, Aeta. 1994, 217, ts. [Fe ™(TPP\(ImPhO)].. crystallizes in a non-centrosym- metric space group, Pna2j, with the normal to the retalloporphyrin ring about 20° off the c-axis. Therefore, ‘net dipole moment or macroscopic polarization parallel to the craxis can be expected only from [Fe%CIPP)- (imPhO)]..- The small size of the doming of the porphyrin in this complex, combined with the large unit cell dimensions, suggests that the spontaneous polarization of (Fe“(TPP\ImPhO)].. will be much smaller than that of BaTiOs2°*-21° The organic portion of the Fe "\(TPP\Im- PhO) polymer does not contribute much to the dipole ‘moment, although it is the major component in the unit cal. jbo. Oa Wee et ane Figure 110. XRD patterns of) Ru[T(p-ChPPI(COXFAOH), (©) a physical mixture of RulT(p-ChPP|(CO)(EOH) and APTES Surfaced moified MCM-41 in a mass ratio of 8:92; (€) 8.3 mass % ABTES surface modified Ru/M.41; and (2) MCM-47 and APTES Surface modified MCMt-41, Reprinted with permission ftom Lu, SG; Pang, W.Q. Che, C:M. Chem. Commun. 1997, 65 sateen HeTPpaacies e HATPPIAMCMLes Figure 111. EPR spectra of photoinduced H,(TPP™) in TIMCM-41, MEMe41 and AIMCM-41 after 30 minutes radiation with ‘Xo 350nm at room temperature. Reprinted wth petmisson frm Sung-Suh, H. Mi; Luan, Z; Kevan, L Phy, Chem, 199%, 701, 10455 18'1997 American Chemical Society Figure 112. Structure of MCIMAP) species. Reprinted with permission from Holland, 8.1; Walkup, C. Stein, A. | Phys. Cham. 8 4998, 102, 4301 © 1998 American Chemical Society eee tae Figure 113. Postlated arangement of the intercalated H(TSPP) inaide the LDH,Chou etal o) Figure 14. Seheraticreprerentaton ofthe (TeCPP)*~ (@) and (acPP)*~ (by oriented inthe interlayers of LDA, . PORPHYRIN-BASED CHEMICAL SENSORS Because oftheir inherent stability, unique optical properties, and synthetic versatility, porphyrins and metalloporphyrins are excellent candidates for a variety of sensing-materials applications. Research in this area has focused on incorporation of synthetic porphyrins and metalloporphy- tins into a variety of material massices, such as polymers, glasses, and LB films, Substantial work has been done in the areas of solution and gas-phase sensing, and highlights of ‘both aceas will be discussed. We will also briefly examine molecular recognition and receptor studies, becuase devel- opments in these areas will further the development of porphyrin-based sensing materials. r) ‘4 fy ery M=Fe,Co,Ru U'= pyz: plo, bpy. dabeo, tz, Bpyac,citoh yr ‘ Ay ‘ a L= ON, SON, NS Mt Fe, Co, Bu, Mn, Cr aos o ore a wy OF DaG-Oo~ = faren ras Figure 115. Various "sigh kebab” one-dimensional coordination polymers 1. Gas Sensors Considering the well-understood ability of heme to bind a vatiety of gases such a5 NO, CO; and Oz, porphyrins would indeed seem a suitable choice for the detection of gaseous species. During the 1990s, much work has been done involving the porphyrin-based detection of a series of gases, such as oxygen, ammonia and chlorine. In addition, recent ‘work has entailed utilization of metallopomphiysin arcay’ for the detection of organic odorants such as amines, thiols and phosphines, Many gas sensors take advantage of analyte iimding to the porphyrin metal center, which gives 2 detectable optical change. Other methods, such as the use of piezoelectric substrates coated with porphyrin films, have also been utilized for gas detection, a. Oxygen ‘The use of metalloporphysin-based materials for the detection of moleclar oxygen is well developed. One approach that has been employed extensively involves the well-known phenomenon of quenching of metalloporphyrin phosphorescence by O2, Due to their high phosphorescence quantum yields and short triplet lifetimes, plasiaum and palladium porphyrins were originally suggested as probesFigure 116. linearly conjugated porphyrin tetramer, Figure 117. porphyrin pohmersytesze athe Heck reaction, or oxygen by Eastwood and Goutérman2" The quenching of porphyrin phosphorescence is described by the Stem- Volmer relationship: ffl = 1+ Kefp 03) Oy where Iy and I are che phosphorescence intensities in the absence and presence of the quencher, respectively; Ke is the Ster—Volmer constant; and pO» isthe partial pressure ‘of Op, Since {/Ke. is equal to the pOa level at which the phosphorescence intensity is reduced by 50%, it is ‘commonly reported as a characteristic for oxygen detectors. Clearly, Kyy will be highly dependent upon the oxygen permeability of the matrix in which the porphyrin is immobilized. Hence, much of the research i this area focuses on these matrices, such as polymers or sol-gel lasses, and on the synthesis of new porphyrins. Okura and coworkers have utiized sol-gefs to make optically transparent glasses containing P(OEP).””? This approach is aimed at creating chemically inert, photostable ‘ateriais which can be used in a Vatiety of environments. As shown in Figure 125, the response is rapid, with a 5-second 90% response time (too). Reversibility was demonstrated ‘upon exposure to 100% nitrogen followed by 100% oxygen. ‘The sensor shows nearly linear behavior ofa range from 0 to 100% oxygen concentration, hut no estimete of detection Jimit was given. One major concem with the use of porphyrins for gas sensing 1s photobleaching. In an effort to enhance porphyrin stability coward photodegradation, Wong and coworkers used halogenated platinum porphyrins immobilized inside silicone films as materials for oxygen sensing” The porphyrins, PQTDCPP), PTFMPP) and PUBrTMP), where TDCPP = 5,10,15,20-etra(2,6-4i- chlorophenybporphyrinate, TFMPP= 5,10,15,20-e0(3,5- bisctiffuoromethyl)phenyl)porphyrinate and BryTMP. 5,10,15,20-tetramesiyl-f-octabromoporphyrinate, were chosen to provide enhanced stability due to their increased ‘oxidation potentials compared (0 PUTPP). The best performance was observed for the PtCTFMPP) film, with a (Ky) Value of 37 tors and response time of 24 seconds Stability studies onthe porphyrin/rubber films revealed that, all of the halogenated porphyrins were indeed more stable than PUPP). Aer 48 hours of ilumination, the PICTPP) luminescence intensity was only 43% ofits original Value, while (BryTMP)Pt remained at 93%. Another approach ‘ovanis enhanced stability is the use of porphyrin ketone complexes. For instance, Hartmann and coworkers have utlzed platinam(t and pallagium(ID) ootaethyipespbysin Ketones (Figure 126) in polystyrene matrices for oxygen sensing.*" Films of PUOEPK) have been reported to be ten times more stable, than their PUOEP) counterparts 40 Photodegradation.** The palladium-based sensor gave an excellent (1/ Ky) valve of 0:59 tor Mills and coworkers hve recently employed PUOBP) and PACGEP) ina variety of different encapsulating matrices for the detection of molecular oxygen.¥® Using cellulose soetate busrate (CAB), poiy(methyt methacrylate) (PMMA) and PMMAICAB polymer blends to encapsulate the Porplyrins on glass-slide supports, the researchers studied the Kay and response-time variation with polymer composi- tion, They found that small amounts of teibutyl phosphate (TBP) plasticizer dramatically increased both the sensitivity and response times ofthe film. As shown in Figure 127, both the pin(O) and the response time decrease signticantly togive minimum values about 120 parts per hundred resin (i) of plasticizer. The (/K,,) value for PACOEP) in CAB / Plasticizer was 0.24 tom, while dhe 90% response time was 5.4 seconds Impressive response times for detection of oxygen via luminescent porphyrins have been demonstrated by Calls, Goutecman, and coworkers.””* Using special instrumenta- tion designed to characterize coatings for video luminescent harometry (VLB), the researchers demonstrated subma- Second response times upon exposing immobilized PUOBP) (0 ar at pressures ranging from 0.1 to 200 tore. This type of| system has been studied in an effost fo provide acrodyns- nicists with a method for determining surface pressures during wind-tunnel tests”creat Dialdehyde PPL PP2 Figure 118, Synthesis of conjugated porphyrin polymers vi the Wit reaction. Reprinted with permission rom Jang, B.; Szu-Wai, Y.; Jones J, W. E. Chem. Mater. 1997, , 2031. 0 1981 American Chemical Society. Reversible binding of oxygen to cobalt porphyrins forms the basis for another series of oxygen sensors. Systems involving cobalt porphyrins have employed a variety of signal-transduction techniques, Work by Oblesby, Leighty, Collman et al. has utilized synthetic cobalt porphyrins for surface acoustic wave (SAW) sensing of oxygen.”"* The SAW sensor, which registers a resonance-frequeney dectease upon adsorption of an analyte, is coated with the ‘porphytin, both in the presence and absence of an imidazole or pyridine-containing copolymer. Porphyrins used for the study were the cobalt) _pieket-fence porphyrin, Co(PEP),?” and cobalt(IT)pienie-basket porphyrins, Co(PBP) (Figure 128). The sensor response to oxygen is reversible, though some hysteresis is noted, which is due to slow diffusion of 2 out of the polymer matrix. The ppicnie-basket porphyrins are particularly interesting because they allow easy tailoring of the oxygen-binding constant, either by changing the central metal ion or by altering the length ofthe bridge or “handle.” This allows for sensing over a Wide range of oxygen concentrations. In related studies, Pretsch and coworkers have utilized picket- fence cobalt porphyrins for optical detection of oxygen.”** Immobilized on poly(octylmethacrylate-co-I-vinylimida- zole) or poly(2,2,3,3,4,4,5,5-octafluoropemylmethacrylate-poly2 2 Sestochom ox polys Figure 119. Synthesis of one-dimensional porphyin-ligethiophens polymers. Reritad vith permission from ‘Sogowa, Hs Kunimoto, K; Susumu, K: Taniguchi, Mi; Shimigzu, T"), Am. chem, Soe 1994, 176, 11198. © 1994 American Chemica! Society, o-L-vinylimidazole) polymer membranes, the porphyrin 204m, which gave a 90% response time range of 5~15 fives a readily detectable shift in its visible absorbance seconds. Spectrum upon binding of molecular oxygen. ‘The useful Fange of the sensor is 1-1000kPa oxygen partial pressure, & Other Gases 6r0.1-100% of atmospheric pressure. Optimum response is Porphyrin-based sensors have also been used for the achieved with the fluorinated membrane, ata thickness of detection of gases such as ammonia, hydrazine and NO.18 Chou et al |: | ee | 2b | Sues ae TS TS | Figure 120. Schematic representation ofa feroelectic coordination polymer and dipole moment switching in Figure 121. The dipole moment of metalloporphyrins Narayanaswamy and coworkers have developed optical ammonia-sensing films based upon immobilized Zn(TPP) in silicone rubber. Upon ligation of the metal center, the well-known phenomena of visible and/or fluorescence spectral shifts can be used to quantify exposure to the analyte. The Zn(TPP}-silicone films gave a linear range of 0-8.Sppm NH; with a detection Jimit of 0.7 ppm. The ‘equilibration time upon exposure was found to be 4 minutes ‘with good reversibility of the ligation. This approach, of course, could be expanded to other amines, as well ax to ther ligating vapors. Ammonia detection has also been studied by Valli and coworkers, who have explored LB films grown from a conjugated dimer of nickel(N) octaethylpor- phyrin™> (Figure 129). The films were created by combin- ing the dimer with arachidic acid, followed by deposition onto hydrophobic quartz substrates. Gold contacts. were sputtered onto the film ends to allow for resistivity measurements as 2 function of vapor exposure. As seen in POTENTIALENERGY | oe + RELATIVE POSITION OF METAL TO PORPHYRIN PLANE Figure 122. The doubleawell potential ofthe position ofthe metal atom relative tothe porphyrin core. Figure 130, the sensor demonstrates a series of equilibria as the ammonia concentration is increased in a stepwise fashion, followed by a return to the original resistance Value ‘upon exposure to air. At 500 ppm of NH, the response time 4s 200 seconds, with a recovery time of 500 seconds. The authors postulate thatthe decreased resistivity upon analyte exposure results from electronic holes created in the porphyrin film upon electron transfer to ammonia mole- cles, Detection of nitric oxide has become particularly important in light ofits regulatory role in many physiolo- gical processes. In an example of NO detection via porphytin-based sensors, Malinski and coworkers have used ‘microelectrode sensors Consisting of layers of a polymeric41 [Porphyrin Materials Chemistry é cod} ByCN Cipye 507 Oyo . 66 OpyCO2 pyCO2 aye Lee Ao to tp oop Foye OpyON SSR a at ImaPrO 4Melm a 4MelmH oso" 4Phim — his Figure 123. Three classes ofthe nonsymmeticl bridging Hgands| porphyrin and Nafion deposited on a thermally sharpened carbon fiber ‘Tetrakis(3-methoxy-4-hydroxyphenyl)por- phyrinatonickei(I1) was polymerized onto the fiber electro. chemically from a solution of 0.1 M NaOH containing the monomer The resulting sensor operates based on the electrechemical oxidation of NO at the porphyrin-doped electrode. A 10-ms response time and a detection limit of, 19nM have been observed, and the sensor has been applied to NO analysis from single endothelial cells in the pulmonary artery as well as to NO quantitation in the blood, Porphyrin Array Vapor Detectors Aray-based sensing has emerged as a powerful approach to vapor detection. Combinations of chemically diverse sensing elements are capable of responding to a variety of analytes. Materials such as polymers, functionalized self assembled monolayers, metal oxides and dendrimers have been used in electronic devices via coupling with piezo- lectric, SAW and semiconductor transducers. In notable ‘examples, Lewis and coworkers have utilized composites of ‘carbon black and polymers for electronic sensing, ** while immobilization of fluorescent dyes in polymer matrices has allowed for optical detection of nonligating vapors by Walt etal.*® Much of the work in this area has been driven by a desire (0 mimic the mammalian sense of smell, which is based upon a large family (approximately 1000 members) of receptor cells*2” More than half of the receptors respond (0 any given odorant exposure? and create a temporal- response signature that is mapped in the olfactory bulb and interpreted by the brain While much work has been done for the detection of nonligating organic odorants, detection of metal-ligating vapors via array-based sensing has been less explored Included inthis class of analytes are noxious ligands such as amines, phosphines and thiols, as well as more toxic substances, for example, nerve toxins such as Tabun, Due 10 their synthetic versaiity and excellent chemical and thermal stability, metalloporphyrins are a natural choice for the detection of such species. Natale and coworkers have uslized metaloporphyrin films in piezoelectic-sensing arrays, where they have shown some success in detection of ligating vapors and determination of food quality.°?"° ‘Theit approach has been to coat quart crystalline micro- balances. with an array of porphyrins, consisting of Ru(TPP}CO), RACTPPICI, " Ma(TPP)CI, — CofTPP), Sn(TPP)CIs, CoCTpNOPP), Co(Tp-OCHsPP) and Mn- octametiyicorole. Responses to different ligating species ‘occur upon ligand binding, which induces mass changes detectable by the microbalances. As seen ix Figure 131, the array shows high sensitivities fora series of ligating vapors, though the response i Himited for alcohols and sufur-based ligands. This type of array has been applied tothe quality evaluation of several types of foods such as fish, meats and Suslick et al. have recently exploited the colorimettic properties of metalloporphyrin arrays for detection of 19120 Chou etal ANTIPARALLEL Figure 124. Tarp alignments of bring igands in metalloporphyrn polymers and ORTEP plots of the pecking sagrame, various ligating vapors 2"! Metalloporphyrin-visible spectra are known to exhibit shifts in wavelength and intensity upon binding of axial ligands. These shifts produce color changes that are often dramatic. The color cbanges are dependent "upon a variety of factors, but vary in large part based upon i rr fe j > ° 0 1 0 300 9a nwt Figure 125. Response of PROEP)teped sat gel glass on switching ‘between (3) 10095 itzagen and (b) 1005 oxygen. Reprinted wath petmisian from Lee, 5 Okura, | Anabst 1997, 122, 81 the degree of polarizability of the analyte 22> Upan exposure to a given analyte, therefore, an array of rmatalloporphyrins is expected o give a unique color-change signature. A series of metalated tetraphenylporphyrins was prepared and spotted onto areverse-phase silica gel plate 10 ive the detector shown in Figure 132. Subtraction of Scanned images taken before and after exposure to analytes gives the color-change profiles observed. All of the vapors Mudied reveal unique color-change pattems. Particularly notable i the fact that ligands of similar funetionality, such as pyridine /hexylamine, or n-tibutylphosphine /triethy!- phosphite, are readily distinguishable. Analyte concentra: tions of less than I ppm can be detected by the aay. Figure 126. A metaloporphyin ketone, MOEPE) Rs Ca41 /Porphyrin Materials Chemistry Figure 127. Variation of (=) pyo(0,) and (b) to wth TBP plasticizer content. Reprinted with permission from Ml, A; Lepee, A. Anal ‘Chem 1997, 69, 4853. © 1997 American Chemical Soret. Ongoing work with this system involves incorpor functionalized metalloporphyrins, such as dendrimer-metal- loporphyrins, which will be discussed later 2. Sensors for Solution Species Porphyrin-based materials have been widely applied toward the analysis of several types of solution species, including ions and organic analytes. Much of the research in these Figure 129. Structure ofa conjugated NQOEP) dimer. 200 SB opm NM, e 200 é ' 8 500 anc 4 90 é lan so! 0 2000 4000-6000. 000 Time (s) Figure 130. Langmuir Blodgett film sensor response at varying NH concentrations. Reprinted with permissior fram Nappa, M. Valentine, 5. At. Chem: Soc. 1978, 700, 5075. © 1978 American Chemical Society areas is based upon incorporation of metalloporphyrins into electrode membranes, where ion-porphytin interactions can bbe monitored potentiometrically, or where electrochemical reactions with analyte substrates can be mediated by the porphyrin. As with gas sensors, this is @ research area where ‘molecular-recognition studies will allow for continued progress. Figure 128. Colas “plenic basket" porphyrins.12 Chou etal Figure 131. Response of porphyrin array towards 14 chemical species, Reprinted with permission from Natale, ©. Macagnano, A; Repole,G. Saggio, G; D/Amico, A; Paolesse, R; Boschi, T. Mater Se. Eng. 1998, 5, 208, «a, Anion Detection Detection of anions in solution via potentiometric techniques has been widely studied. If lipophilic elec- trode-membrane materials are employed, the selectivity of the detector is based upon the solubility of the anions in the ‘membrane layer. This gives rise to the Hofmeister pattern, whereby lipophilic anions are preferentially incorporated into the membrane, in the order CIO, >10; > 1” >Br- >Cl~ >HCO; 2 Deviation from Hofmeister selectivity can be achieved by incorporating a range of ‘compounds, including porphyrins, metallocomrins and phthalocyanines, into the membrane. The varying affinities that anions have for the chosen macrocycle metal center can ‘change the ion preference of the material. Porphyrins are also utilized because their synthetic versatility allows for creation of size-selective pockets about the metal center, lending additional selectivity. For instance, Meyerhoff and coworkers have examined various synthetic ‘manganese porphyrins by incorporating them into PVC polymer membranes.® The porphyrins, shown in Figure 133, were chosen to give a wide range of steric access and/or hydrophobicity to the metal-center anion-ligation site. The tetraphenylporphyrins (Figure 133) deviate from the Hofimeister tend due to selectivity imparted by axial binding to the manganese center. The tetrahalonaphthylpor~ phyrins (Mn(TXNP)C) are even more exclusive of Perchlorate and iodate, owing to their more hindered metal centers. Meanwhile Mn(TDDPP) Cl and. Mn(TDDIP)CI, which contain nitrogenous axial ligands, destabilize anion coordination to the metal, restoring the Hofmeister selec- tivity. Improved affinity for salicylate was subsequently achieved by incorporation of Sn(TPPJCIy into the electrode membranes." Zheng and coworkers have employed a similar method- ology and have demonstrated that PVC membranes doped with indium tetraphenylporphyrin show high relative sensitivity to nitrite ions” Manganese and indium porphyrins immobilized in silicone by Paeng et al. have been used for the potentiometric analysis of serum chloride levels." Studies of synthetic porphyrin-based anion receptors should form the basis for more effective sensors. Metallo- cene-substituted porphyrins examined by Beer and co- workers have proven successful in the solution-phase binding of ions such as chloride, bromide and nitrate.” ‘The cobaltocenium-substituted and ferrocene-substtuted porphyrins (Figure 134) bind ions in solution, as shown by HNMR and electrochemical studies, The latter measure~ ‘ments reveal that the porphyrin and ferrocene redoxlens Foo Gob] 6 ®@ late Pyridine Hexylamine Triethyl- —Tributyl- phosphite phosphine Ethanol Hexane- thiol Dipropyl- sulfide Figure 132. Black and white projection of colar change fingerprints fora seres of lgating vapors. In color, the diferences between analytes are considerably more distinct. potentials vary with the bound ion. Studies of the various atropisomers of the ferrocene-substituted zine porphyrin have shown interesting isomer-dependent selectivities, For example, the au2B isomer shows a preference for nitrate over chloride, where the other atropisomers show a preference for spherical ions such chloride and bromide. In related work, Sessler and coworkers have shown sapphyrins to be potentially useful receptors for anion sensing. These expanded species are more basic than their porphyrin counterparts, and hence readily forin dicationic species in solution.”*° The positively charged dication cote forms a site for anion binding. A deca-alkyl sapphyrin was originally shown to bind fluoride ion, as shown by the crystal structure in Figure 135. The ion is believed to be stabilized via @ combination of electrostatic and hydrogen: bonding interactions, In more recent studies, Sessler er al have found that sapphyrins appended to silica gel show high affinities for phosphate and arsenate, as well as an ability to separate a wide range of anionic ‘species when used as HPLC solid phases.™? These types of materials may be applicable to more specific anion-sensing applications, ‘4. Cation Detection While detection of cations via porphyrin-based materials has been explored less than anion sensing, the ability of a porphyrin to coordinate different metals and the unique spectral signatures that result form the basis for metal ion detection. Use of free-base porphyrins in polymer matrices has allowed for the detection of heavy metal ions by Ache et al.®* Immobilization of 5,10,15,20-tetrakis(4-N- methylpyridyDporphyrin on Nafion membranes permitted detection of cadmium and mercury in solution with dete ction limits of 5 x 10-*M and 2 x 10~"M, respectively over a 20-minute measuring period. The method is subject to interferences from other metal ions, but the researchers were able {0 detect several ions simultancously using pattern-recognition techniques such as principal component analysis. Sol-gel films doped with 5,10,15,20-tetra(p- sulfonatophenyDporphyrin have also been used by Ache and coworkers for the fluorimetric determination of mercury in solution, with a detection Kimit of approximately Tx 107? M2 Porphyrin-doped electrodes have been employed for the electrochemical and potentiometric detection of nickel(T) in aqueous solutions. Malinski and coworkers have utilized polymeric tetrakis(3-methoxy-4-hydroxyphenyl)porphyrin, H,(TMHPP), film electrodes for nickel determination.” The films are grown by electrochemical deposition from a solution of 0.1M NaOH containing 5x 10-* M NiCTMHPP). The film is then demetalated in acid solution, yielding a polymer that the authors postulate to have enhanced selectivity for nickel cations due to its formation from the nickel monomer. Using differential pulse voltam- metry to monitor the Ni(ID/ Ni(II) oxidation, a detection limit of 8 x 10~*M was obtained for a 60-second exposure to anickel containing solution. The calibration curve shown in Figure 136 shows linear response over a range of 10~7 to 2.x 10~°M. In the presence of interferences, for example, zinc(ID), cadmium(ll) or copper(II), some reduction in Signal is seen; however, no ion showed redox activity in the region of detection. Gupta and coworkers have utilized Ha(TPP)and HCTTP) in PVC-based membranes for the potentiometric detection of nickel(I).° The sensor ‘demonstrated lincar response in the range of 5.6% 10 1.0.x 107'M, with a response time of 20 seconds. The primary observed interferences were Co* and Na ions. Quantitative determination of Ni** in chocolate samples using this detector gave good agreement with values obtained from atomic absorption spectroscopy. 6. Sensors for Organic Molecules Many current organic molecular sensors employing metalloporphyrins are based upon the ability of the 41 JPorphyrin Materials Chemistry SSS 123124 Chou et al Mn(TDDPP)CI Mn(TDDIP}CI Figure 133. Structures of quaternary ammonium and manganese metallaporphyrin specles use for membrane preparation. porphyrin to act as a catalyst forthe reduction or oxidation of organic substrates. This concept has been used by Saini and coworkers, who have recently used porphyrin-modifed electrodes for the determination of organohalide species in aqueous solution.” By precipitating (TPP)Co ona sgraphitefoil working electrode, the researchers were able {0 induce the reduction of various organohalides, such as carbon tetrachloride, perchloroethylene and iodobenzene. The sensor is believed to function via a porphyrin-mediated, two-electron-reduction pathway shown below Co (TPP) + 6° -+ Col(TPP) Col( TPP) + RX —+ Col(TeP)(R) +X CCol(TPE)(R) + €° —+ CoMTPP) +R ‘Amperometric studies, with a working potential of “= 500 mV, gave a detection limit of 0.75 ppm for carbon tetrachloride. The amperometric calibration curves for carbon tetrachloride and perchloroethylene are shown in Figure 137, Greatest sensitivities were seen for haloalkanes, with less sensitivity for haloalkenes or haloarenes. Inter ference from nonhalogenated organics (e.g, ethanol, allyl alcohol or phenol) was not seen, although the addition of phosphate ion gave sligit decreases in response intensity. In related work, Priyantha and Weerabalt used Fe(TPP)CI for the amperometric detection of the herbicide propanil.”** ‘The porphyrin was coated on a glassy carbon working electrode, which was used for the reduction of 3,4- dichloropropicaanilide, the msin component of the hetbi- cide. The resulting detector exhibited a detection limit of 80 pM. ‘As alluded to earlier in this section, studies of molecular receptors figure to provide a series of new sensors, particularly for the detection of solution-phase species, ‘Towanls this end, a series of porphyrin complexes and assemblies have proven successful in assessing the selective binding of organic molecules, Design of shape-selective binding pockets and hydrogen-bonded arrangements have proven especially successful using macrocyclic oligosac- charides. By using porphyrins as displaceable substrates of the binding sites, relative binding analysis of other analytesFigure 134, Metallacene containing porphyrins fr anion recogni tion, Reprinted with permission from Betr,P. Dj Orem MG. By Hesek, By Jagessay, 1. chem, Soe, Chem. Comm. 1995, 1187, Figure 135, Molecular structure of decay sapphyrin binding fluoride ion. Reprinted with permision from Sessler, | Lz Cj, M. fs lynch, Vi; McGhee, E; bers, ]-A. JA. Chem. Soc. 1990, 112, 2810. 41 J Porphyrin Materials Chemistry 1235 od Concantation at Figure 136, Response of TMHP? flm-based nickel sensor at varying concentration. Reprinted with permsion fram Malin, {Ciszewshi, A; Fishy 8; Cauchajowsi L. Anal. Chem, 1990, 62, 909. '@ 1990 American Chemical Society [Sosa Figure 137. Response of CocTPP)/graphite electrode to carbon tettachioride (CT) and perchloroetivlene (PCE). Reprinted with petmision rom Dobson, D. J; Saini, S. Anal. Chem. 1997, 69, 3832. '5'1997 American Chemical Society Figure 128. porphyrieylcholate bow, Reprinted wth permis sion fom Bonar Mackay, Gy Sanders :M. Chem Soe, Cher Conn 1993, 436.126 ‘Chou et a. Figure 139. Cyclodextrn-porphyrin assembly for recognition of penlachlorophenol. Reprinted with permission fom Zhao, S. Luong, [HLT [-Chem. Soc, Chem. Comm. 1995, 663. can be monitored through visible spectroscopy, since displacement of the porphyrin from within the macrocyele can produce observable spectral shits, For instance, ‘morphine recognition has been probed by Sanders and coworkers via the synthesis of a porphyrin-cyclocholate molecular bowl, shown in Figure 138." Compared to tetrakis@-methoxyphenyDporphyrin, which was used as a reference compound, the bow shows a binding constant for morphine 3.8 x 10? times higher, resulting from favorable hydeogen-bonding interactions. between the owl and morphine molecule. The bow! also binds other amines such a8 codeine and pyridine, but with lower binding constants than for morphine. In’ similar fashion, a cyclodextin porphyrin assembly has been demonstrated to have high selectivity for pentachlorophenol (PCP) by Luong and coworkers? Shown in Figure 139, the assembly. is organized via hydrogen bonds between the carboxylic acid groups ofthe teracarboxy porphyrin and hydroxy groups on the cyciodextrin, PCP is well suited for the cyclodextrin- porphiyzin asembly cavity, due to its proper size, sufficient hydrophobicity and hydroxy! group, which can’ hydrogen bond to the pyrrole nitrogens of the porphyrin. Visible spectroscopy studies of Soret band shifting upon binding showed that ofa range of chlorinated aromatic species, only PCP and 2,3,5,6-tetrachlorophenol exhibited binding. ocks . OH Cy om #0 be 8-04 HOP on denotes saccharide :@ Figure 140. Binding of saccharides to a boronicacid containing receptor. Reprinted with permission from Takeuchi, ML Kina, H. Hamachi, shintal,S. Bull Chem. So. Jpn. 1997, 70, 699 Shinksi and coworkers have created a unique sugar- sensing system based on the cooperative interactions of two boronic-acid-receptor moieties *! The first is linked to a zine tetraphenylporphyrin, and the second to a coordinated pyr xling of saccharides to the porphyrin-pyridine complex, as shown in Figure 140, produces spectral shifts Studies in which solid sugars were extracted into dichloro- ‘methane solutions containing the receptor were conducted, and percentage of extracted sugar Was determined via circular dichroism spectrscopy. Among a series of sugars, the highest affinities were seen for D and L. configurations of fructose and arabinose. Dendrimer-porphyrins are another class of molecular receptors which have been recently demonstrated to have interesting. shape-selective ligand-binding capabilities by Suslick et al.2#? Linking of first- and second-generation carboxylic acid dendrons to zine tetrakis(3.5-dihydroxy- phenyl)porphyrinate and zinc tetrakis(2,6-dihydroxyphe- nyDporphyrinate produced a series of dendrimer metal- loporphyrins (Figure 141). Quantitative determination ofthe binding constants of nitrogenous bases t0 the zinc were made using visible spectroscopy. ‘The meta-substituted dendrimer porphyrins interestingly show increased affinity for the bases relative to unhindered Zn(TPP), a phenomenon due to favorable interactions between the amines and the aromatic dendrimer structure. The ortho-substicuted den- drimer porphyrins, however, showed excellent shape selectivity, as demonstrated by the log(K.,) values (Figure 142), Particularly striking forthe ortho-substituted dendi- mer porphyrins isthe difference in binding affinity between linear and nonlinear amines, such as that between 4 phenylpyridine and quinine (K., difference > 10°). This {ype of selectivity could potentially be exploited in sensors for ligating species in either solution or the gas phase.41 [Porphyrin Materials Chemistry Figure 141. Molecular models showing a side view of the binding sites of dendiimer porphyrins. Top: meta-substituted HTS G1P)). Botton: ortho substituted denckimer-porphyrin HCH! CGIAP)P. Note the open cavity of = 10A versus a narow shit of =: respectively in both cases, top access to the porphyrin s completely Blocked IV. Conclusions Because of their synthetic versatility and chemical robust- ness, porphyrins and metallaporphyrins are proving to be very useful platforms on which to tailor field-responsive and chemo-responsive materials, Diverse applications of por~ phyrins and metalloporphyrins (9 materials chemistry have been developed over the past decade, both for their optical properties and their applications as sensors. Notably, porphyrins and metalloporphyrins have found applications as feld-responsive materials, particularly for optoelectronic applications, including mesomorphic mater ae ate rcere wrerouee / a ea Ke) Figure 142.ainging of axial igand to dendrimer porphyrins Togtto) vate fora senes of trogenaus bases A varus shepes. als and optical-limiting coatings. Porphyrins show interest- ing second- and third-order NLO properties, due to theit exceptionally large t-electron conjugation’ length, ‘The primary attention has focused on third-order NLO properties ‘and optical-limiting materials, Improvements in the area of, nonlinearity versus transparency trade-off should be possi- ble via molecular engineering. The molecular design of novel porphyrins possessing desired physical, optical and nonlinear optical properties for specific photonic applica- tions remains a difficult, but often rational, challenge. Ingenious designs and newly developed synthetic meth- ‘odologies have also led to significant progress in the development of molecular optoelectronic porphyrinie mate- rials. Long-term stability against photodegradation remains important, however, and may preclude effective devices for many molecular electronic applications. ‘The development of chemo-responsive materials based ‘on porphyrins as highly porous, molecularly based mole- cular sieves or shape-selective solid catalysts is currently under development. Porphyrins and metalloporphyrins have also been examined for a variety of sensor applications, which proves their importance as an emerging class of chemo-responsive materials. The unique spectral character- istics and synthetic versatility of porphyrins allow for a variety of sensing applications. 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