Solr cy Matec lar al 14 (205) 122-02 Contents lists availabe at ScenceDicect Solar Energy Materials & Solar Cells journal homepage: www. elsevier-com/locate/solmat Copolymerisation as a way to enhance the electrochromic properties of an alkylthiophene oligomer and a pyrrole derivative: copolymer of 3,3” dihexyl-2,2:5',2":5",2’"-quaterthiophene with (R)-(-)-3-(1- pyrrolyl)propyl-N-(3,5-dinitrobenzoyl)-o-phenylglycinate Ana Julia C. Silva®®, Viviane C. Nogueira”, Thebano E.A. Santos, Craig J.T. Buck‘, David R. Worrall‘, Josealdo Tonholo**, Roger J. Mortimer‘, Adriana S. Ribeiro™“* “tim de Qin tag UnieiateFral de Ago, Cap AC nes, ar do Mar 5727290 Mac A, rit ante de eas rma ema fr Die de espera 08D, Cplas Pr epeemce onary tnepoeag rey Lt stones waee eae Qos ened 23 ue 2008 ‘The copotymerintin of" Dibexy- 225 25.2" -quaerthkphene (OHO) and (®-C) pyr IMipropy3.5-diuobenzoy-a-pieryalnte (ONS) was succesfully perfred electron ‘lly in acetonitrile (CH,CH) containing terabutylaromoniittraloorobarat (CL). hy direct ‘xiatlon of manomer mintres in dilerent ee ratios Copolymersaton mpraved the opertes Othe ims ot both polynes POHGT and PONE, in respect to the aceson of POAT onto Oya sutace and the chroman contrast of these electochromie mates. POAGT, PON? and (DMT -o-DNP) Fis were characterised by FDR spectoscpy rescence specrosop, Sannin Elton Mroseopy (Scho apa specrokectroehemseal tengo. Sations of PONT and is eopayrners with DAB? (edependeaty fhe eed ati} N-metiyyraidne are resent with ems hands a 55 and 585 nm when ected at 375, Reverie changes nthe hue and aration teu i alte copay ims from yellow or orange inthe reduced stat to green or blue inthe ised state, Dut were ‘pendent on the proportion of the comanomers used to prepare the copolymers. These changes are ‘more slgnicat for (DHT or 02 03 Oa as (Vs. Agiag’) i.e vtammograms of PONT) and HT <-DNBP ns epested molting dens | an 7 bed ene Siro (CNMEACHLEN 20.5 ‘omic pst ptt Abate peak pt yan a tc (00) fat led (GV) Ses nd pe 6) oe pre ie Ta) How) Em) fmt) Saar ea 2 near infrared region (NIR, above 800 nm) was identified for all ‘copolymer films. This reveals the formation of bipolarons,atrib- tuted tothe highly conducting state of the polymer fim [51,52 'As can be seen in Table 1, comparison ofthe band gap energy () values (estimated from the optical absorption edge in the ‘onset ofthe x-x" transition ofthe Alm inthe neutral state using ‘the Tae elation [5354] See Fg. 1 in Supplementary Information) ‘obtained for PDHQT, the copolymers, and PONE? shows that intreiction of DNBP into the PDHGT chain led to an intermediate v= value for the copolymers. Furthermore, the E, value for POAT (197 eV) is quite lower than that caleuated by Facehett etal [44] for the DHQT (288 eV), indicating that even with the ‘dissolution of oligomers during the electrpolymerisation proces, 4 conjuzated chain is deposited onto the electrode surface. The description of colour, or the comparison of two colours isa subjective process and iis dificult wo describe this accurately. So in order to ive a better interpretation of the changes in the spectral absorption bands according to the potential applied to the ‘stem, the CIE 1931 ay chromaticity coordinates were calculated from the in situ spectra of each fl and their trajectories for PDHGT, RDHOT-co-DNBP) deposited onto MTO/glass in diferent proportions and PONBP are shown in ig. 8 (See aso Tales 1-36 and Fig. $2 in Supplementary information). W can be clearly seen that whilst the colour variation forthe films of PDHOT, PONRP and P{DHOF-co-DNAP) deposited onto FDjelase with 1:1 feed ratio ks ‘very low the other copolymer fis presenta remarkable change in their colour according othe applied potential In this ease their romar rome. Date 1 Tsan vette {ria decempedalis ‘epost do Os wi aren ee me oe & ——— Te easomnn SB B ew recom So ae meaner a me mt owgrce-oMae) i 000 wee oe me OUT lw Similarly to the analysis of the morphology of the films, the ‘characterisation by fluorescence spectascapy has helped to obtain ‘sition information about the sacture ofthe copolymer, sieges ing the formation of 2 Bock copolymer. Furthermore, Nuoresence measurements show tht the PDHOT and its copolymers with DNBP ‘are good yellow light emitters. The enhanced electrochromic proper ties ofthe NDHQF-co-DNOP) copolymer films are interesting for the pplication of these materials as active layers in optoelectonic ‘devices, such as displays and smart windows Therefore, the combi nation of DHQT and DNBP makes these structures usefl for promis- ing applications as elecwehwomic and fluorescent materials ‘Acknowledgements “The authors wish to thank the granting authors CNP, CAFES. [BNE (FUNTEL and CTENERG Programs), FAPEAL, INCT INAMICN {and INCTINAMI|CAPES/Nanobiotchnology for financial support and for ellowship to AICS (BNCT INAMIJCAPES/Nanobiocetnokogy) JF and {ASR (INCFINAMICNPS, Scence without borders: LNLS (National Sychraron Light Laboratory, Campinas SP) for the use of scanning ‘leon microscope and Braskem Ca. (ral) forthe prenership i the etd of cente and tecnologcal development. [Appendix A. Supporting information Supplementary data associated with this article can be found in the online version at hip|dxdoLory10J016)solmat 20141037, References 18 Mine: i ctu in bin 44898) [2] Fs en), Maca, 08 asc, Hectrcomion nde Mare 4 (202) 3 HL Thompson sian Zon. Leys. neler Says ferme pms an Snes Chom Ms E00) UE Hoye za. 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