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postgraduate thesis: Design and synthesis of functionalized alkynylplatinum (II) polypyridyl complexes and oligothienylenevinylene derivatives : from dye-sensitized solar cells to bilayer heterojunction photovoltaics

TitleDesign and synthesis of functionalized alkynylplatinum (II) polypyridyl complexes and oligothienylenevinylene derivatives : from dye-sensitized solar cells to bilayer heterojunction photovoltaics
Authors
Issue Date2012
PublisherThe University of Hong Kong (Pokfulam, Hong Kong)
Citation
Kwok, C. [郭志豪]. (2012). Design and synthesis of functionalized alkynylplatinum (II) polypyridyl complexes and oligothienylenevinylene derivatives : from dye-sensitized solar cells to bilayer heterojunction photovoltaics. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. Retrieved from http://dx.doi.org/10.5353/th_b4775269
AbstractA series of alkynylplatinum(II) polypyridine complexes with 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine and 4,4′-dicarboxy-2,2′-bipyridine as TiO2 anchoring functionalities, has been successfully synthesized. Their photophysical, electrochemical and luminescence properties have been extensively studied. The excited state properties were probed using nanosecond transient absorption spectroscopy. [Pt(tctpy)(C≡C-Th-BTD-Th)][NnBu4]2 displayed a long-lived transient signal which was tentatively assigned to result from the formation of a charge-separated state, which could be alternatively described as a [Pt(tctpy)???(C≡C-Th-BTD-Th)+?] state, with the charge recombination rate constant determined to be 2.9 × 105 s?1. The excited state redox potentials for the oxidation process were determined and the data confirmed the ability of the complexes to inject an electron into the conduction band of TiO2. The majority of the complexes were found to sensitize the nanocrystalline TiO2 and exhibit photovoltaic properties, which have been characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm–2). A new class of molecular dyads comprising metalloporphyrin-linked alkynylplatinum(II) polypyridine complexes was synthesized and characterized. Their photophysical, electrochemical and luminescence properties have been studied in detail. The excited state properties were probed using nanosecond transient absorption spectroscopy which indicated the formation of a charge-separated state involving the porphyrin radical anion, [Por??-(C≡C)Pt+?]. The excited state redox potentials for the oxidation process were also determined with the data supporting the capability of the complexes to inject an electron into the conduction band of TiO2. The majority of the complexes were found to sensitize the nanocrystalline TiO2 and exhibit photovoltaic properties, as characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm–2). A series of organic materials consisting of a triphenylamine-based donor with oligothiophene or oligothienylenevinylene based-conjugated linker and dicyanovinyl, tricyanovinyl or cyanacrylic acid groups as acceptor, was synthesized and characterized. Their photophysical, electrochemical, thermal and luminescence properties were studied. Transient absorption spectra of TPA-OTV-DCN in dichloromethane solution on the pico- to nanosecond timescale were recorded after femtosecond laser excitation at 400 nm. A transient signal at ca. 700 nm was tentatively assigned to result from the formation of a charge-separated [(TPA-OTV)+??DCN??] state with the charge recombination rate constant determined to be 5.3 × 109 s?1. The energy levels of the LUMOs of TPA-OTV1-DCN, TPA-OTV2-DCN, TPA-OTV3-DCN TPA-TAZ1-DCN, TPA-TAZ2-DCN and TPA-o-4Th-DCN were calculated to be of ca. ?3.9 eV, establishing the formation of a downhill driving force for the energetically favorable electron transfer process involving the injection of an electron into the LUMO of the C60 acceptor. The majority of the compounds were found to exhibit photovoltaic properties. The photovoltaic responses were characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm–2).
DegreeDoctor of Philosophy
SubjectPhotochemistry
Complex compounds - Synthesis
Platinum compounds - Synthesis
Dept/ProgramChemistry
Persistent Identifierhttp://hdl.handle.net/10722/208172

 

DC FieldValueLanguage
dc.contributor.authorKwok, Chi-ho-
dc.contributor.author郭志豪-
dc.date.accessioned2015-02-20T23:07:00Z-
dc.date.available2015-02-20T23:07:00Z-
dc.date.issued2012-
dc.identifier.citationKwok, C. [郭志豪]. (2012). Design and synthesis of functionalized alkynylplatinum (II) polypyridyl complexes and oligothienylenevinylene derivatives : from dye-sensitized solar cells to bilayer heterojunction photovoltaics. (Thesis). University of Hong Kong, Pokfulam, Hong Kong SAR. Retrieved from http://dx.doi.org/10.5353/th_b4775269-
dc.identifier.urihttp://hdl.handle.net/10722/208172-
dc.description.abstractA series of alkynylplatinum(II) polypyridine complexes with 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine and 4,4′-dicarboxy-2,2′-bipyridine as TiO2 anchoring functionalities, has been successfully synthesized. Their photophysical, electrochemical and luminescence properties have been extensively studied. The excited state properties were probed using nanosecond transient absorption spectroscopy. [Pt(tctpy)(C≡C-Th-BTD-Th)][NnBu4]2 displayed a long-lived transient signal which was tentatively assigned to result from the formation of a charge-separated state, which could be alternatively described as a [Pt(tctpy)???(C≡C-Th-BTD-Th)+?] state, with the charge recombination rate constant determined to be 2.9 × 105 s?1. The excited state redox potentials for the oxidation process were determined and the data confirmed the ability of the complexes to inject an electron into the conduction band of TiO2. The majority of the complexes were found to sensitize the nanocrystalline TiO2 and exhibit photovoltaic properties, which have been characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm–2). A new class of molecular dyads comprising metalloporphyrin-linked alkynylplatinum(II) polypyridine complexes was synthesized and characterized. Their photophysical, electrochemical and luminescence properties have been studied in detail. The excited state properties were probed using nanosecond transient absorption spectroscopy which indicated the formation of a charge-separated state involving the porphyrin radical anion, [Por??-(C≡C)Pt+?]. The excited state redox potentials for the oxidation process were also determined with the data supporting the capability of the complexes to inject an electron into the conduction band of TiO2. The majority of the complexes were found to sensitize the nanocrystalline TiO2 and exhibit photovoltaic properties, as characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm–2). A series of organic materials consisting of a triphenylamine-based donor with oligothiophene or oligothienylenevinylene based-conjugated linker and dicyanovinyl, tricyanovinyl or cyanacrylic acid groups as acceptor, was synthesized and characterized. Their photophysical, electrochemical, thermal and luminescence properties were studied. Transient absorption spectra of TPA-OTV-DCN in dichloromethane solution on the pico- to nanosecond timescale were recorded after femtosecond laser excitation at 400 nm. A transient signal at ca. 700 nm was tentatively assigned to result from the formation of a charge-separated [(TPA-OTV)+??DCN??] state with the charge recombination rate constant determined to be 5.3 × 109 s?1. The energy levels of the LUMOs of TPA-OTV1-DCN, TPA-OTV2-DCN, TPA-OTV3-DCN TPA-TAZ1-DCN, TPA-TAZ2-DCN and TPA-o-4Th-DCN were calculated to be of ca. ?3.9 eV, establishing the formation of a downhill driving force for the energetically favorable electron transfer process involving the injection of an electron into the LUMO of the C60 acceptor. The majority of the compounds were found to exhibit photovoltaic properties. The photovoltaic responses were characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm–2).-
dc.languageeng-
dc.publisherThe University of Hong Kong (Pokfulam, Hong Kong)-
dc.relation.ispartofHKU Theses Online (HKUTO)-
dc.rightsCreative Commons: Attribution 3.0 Hong Kong License-
dc.rightsThe author retains all proprietary rights, (such as patent rights) and the right to use in future works.-
dc.subject.lcshPhotochemistry-
dc.subject.lcshComplex compounds - Synthesis-
dc.subject.lcshPlatinum compounds - Synthesis-
dc.titleDesign and synthesis of functionalized alkynylplatinum (II) polypyridyl complexes and oligothienylenevinylene derivatives : from dye-sensitized solar cells to bilayer heterojunction photovoltaics-
dc.typePG_Thesis-
dc.identifier.hkulb4775269-
dc.description.thesisnameDoctor of Philosophy-
dc.description.thesislevelDoctoral-
dc.description.thesisdisciplineChemistry-
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.5353/th_b4775269-
dc.date.hkucongregation2012-

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