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Push-Pull N,N-Diphenylhydrazones bearing bithiophene or thienothiophene spacers as nonlinear optical second harmonic generators and as photosensitizers for nanocrystalline TiO2 Dye-Sensitized solar cells
A series of push-pull heterocyclic N,N-diphenylhydrazones were prepared to study the effect of structural modifications (different pi-spacers and electron withdrawing groups) on the optical (linear and nonlinear) and electronic properties of the molecules.The photovoltaic response of DSSCs assembled using nanocrystalline titania photosensitized with the synthesized dyes was also studied. These heterocyclic push-pull conjugated dyes involve N,N-diphenylhydrazones as electron donors linked to bithiophene or thieno[3,2-b]thiophene spacers, and were functionalized with carboxylic acid, cyanoacetic acid, or dicyanovinyl acceptor groups. A combination of Suzuki-Miyaura cross-coupling, Vilsmeier formylation, and condensation reactions were used to synthesize the intermediates and final products. DFT and TDDFT calculations were used to obtain information on conformation, electronic structure and electron distribution, both for the free dyes and those adsorbed on TiO2. The results of this multidisciplinary study indicate that dyes 5b and 6b have the strongest second order nonlinear optical response with hyperpolarizability values in the range of beta = 2330-2750 × 10-30 esu, while photovoltaic power conversion efficiencies reach values in the range of 0.7-3.0 %, for dyes 5a-b and 7c that were enhanced by co-adsorbing DCA (0.8-5.1 %). ; Thanks are due to Fundação para a Ciência e Tecnologia (FCT) for a PhD grant to S.S.M.F. (SFRH/BD/87786/2012). To FEDER-COMPETE for financial support through the research center CQUM (UID/QUI/0686/2016). The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project no. 022161 (cofinanced by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). The group in Coimbra is grateful for funding from Centro de Química de Coimbra which is supported by the Fundação para a Ciência e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the programmes UID/QUI/ UI0313/2013 and COMPETE. The authors also thank the Laboratory for Advanced Computing at the University of Coimbra for providing computing resources that have contributed to the research results reported in this manuscript. Thanks are also due to FCT for a postdoctoral grant to L.L.G.J. (SFRH/BPD/97026/2013). The group in Porto would like to acknowledge the European Commission through the Seventh Framework Programme, the Specific Programme “Ideas” of the European Research Council for research and technological development as part of an Advanced Grant under grant agreement no. 321315, which also partially funded this work. Some of this work was also performed under the project “SunStorageHarvesting and storage of solar energy”, with reference POCI-01-0145-FEDER-016387, funded by European Regional Development Fund (ERDF), through COMPETE 2020Operational Programme for Competitiveness and Internationalization (OPCI), and by national funds, through FCT. ; info:eu-repo/semantics/publishedVersion
Push-Pull N,N-Diphenylhydrazones bearing bithiophene or thienothiophene spacers as nonlinear optical second harmonic generators and as photosensitizers for nanocrystalline TiO2 Dye-Sensitized solar cells
A series of push-pull heterocyclic N,N-diphenylhydrazones were prepared to study the effect of structural modifications (different pi-spacers and electron withdrawing groups) on the optical (linear and nonlinear) and electronic properties of the molecules.The photovoltaic response of DSSCs assembled using nanocrystalline titania photosensitized with the synthesized dyes was also studied. These heterocyclic push-pull conjugated dyes involve N,N-diphenylhydrazones as electron donors linked to bithiophene or thieno[3,2-b]thiophene spacers, and were functionalized with carboxylic acid, cyanoacetic acid, or dicyanovinyl acceptor groups. A combination of Suzuki-Miyaura cross-coupling, Vilsmeier formylation, and condensation reactions were used to synthesize the intermediates and final products. DFT and TDDFT calculations were used to obtain information on conformation, electronic structure and electron distribution, both for the free dyes and those adsorbed on TiO2. The results of this multidisciplinary study indicate that dyes 5b and 6b have the strongest second order nonlinear optical response with hyperpolarizability values in the range of beta = 2330-2750 × 10-30 esu, while photovoltaic power conversion efficiencies reach values in the range of 0.7-3.0 %, for dyes 5a-b and 7c that were enhanced by co-adsorbing DCA (0.8-5.1 %). ; Thanks are due to Fundação para a Ciência e Tecnologia (FCT) for a PhD grant to S.S.M.F. (SFRH/BD/87786/2012). To FEDER-COMPETE for financial support through the research center CQUM (UID/QUI/0686/2016). The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project no. 022161 (cofinanced by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). The group in Coimbra is grateful for funding from Centro de Química de Coimbra which is supported by the Fundação para a Ciência e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the programmes UID/QUI/ UI0313/2013 and COMPETE. The authors also thank the Laboratory for Advanced Computing at the University of Coimbra for providing computing resources that have contributed to the research results reported in this manuscript. Thanks are also due to FCT for a postdoctoral grant to L.L.G.J. (SFRH/BPD/97026/2013). The group in Porto would like to acknowledge the European Commission through the Seventh Framework Programme, the Specific Programme “Ideas” of the European Research Council for research and technological development as part of an Advanced Grant under grant agreement no. 321315, which also partially funded this work. Some of this work was also performed under the project “SunStorageHarvesting and storage of solar energy”, with reference POCI-01-0145-FEDER-016387, funded by European Regional Development Fund (ERDF), through COMPETE 2020Operational Programme for Competitiveness and Internationalization (OPCI), and by national funds, through FCT. ; info:eu-repo/semantics/publishedVersion
Push-Pull N,N-Diphenylhydrazones bearing bithiophene or thienothiophene spacers as nonlinear optical second harmonic generators and as photosensitizers for nanocrystalline TiO2 Dye-Sensitized solar cells
Fernandes, Sara S. M. (author) / Belsley, M. (author) / Pereira, Ana I. (author) / Ivanou, Dzmitry (author) / Mendes, Adélio (author) / Justino, Licínia L. G. (author) / Burrows, Hugh D. (author) / Raposo, M. Manuela M. (author)
2018-01-01
doi:10.1021/acsomega.8b01045
Article (Journal)
Electronic Resource
English
DDC:
690
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