Investigation on intramolecular charge transfer in π-conjugated donor and acceptor ensembles
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Abstract
π-Conjugated donor (D) and acceptor (A) ensembles have been widely investigated in the fields
of (bio)chemistry, physics, medicine, materials chemistry and nanoscience because of their
unique optical and electrochemical properties. Electronic interactions between D and A units
have been widely explored for the development of advanced functional materials. Therefore,
diverse π-conjugated ensembles containing different donors such as benzodifuran (BDF),
tetrathiafulvalene (TTF), triphenylamine (TPA), and acceptors including 2,1,3-
benzothiadiazole (BTD), perylene diimide (PDI), tetraazapyrene (TAP) and
dipyrrolylquinoxaline (DPQ) have been investigated. It has been demonstrated that HOMO
and LUMO energy levels and band gaps critically depend on the intrinsic electronic properties
of D and A units as well as the nature of the linker between them. To optimize the electronic
communication between D and A units for potential applications in molecular (opto)electronics,
a variety of π-conjugated ensembles with different D-A architectures have been designed,
synthesized, and characterized in this thesis. Importantly, efficient synthetic approaches to
functionalize the TAP core via halogenation, hydrolysis, oxidation, and condensation have
been developed, allowing the preparation of various kinds of TAP-based D-A molecules. Our
keen interest in such π-conjugates has led us to comprehensively investigate the intramolecular
charge-transfer (ICT) interactions through-bond or through-space between D and A moieties
by UV-Vis-NIR spectroscopy, cyclic voltammetry (CV), transient absorption spectroscopy
(TAS) and density functional theory (DFT) calculations.
of (bio)chemistry, physics, medicine, materials chemistry and nanoscience because of their
unique optical and electrochemical properties. Electronic interactions between D and A units
have been widely explored for the development of advanced functional materials. Therefore,
diverse π-conjugated ensembles containing different donors such as benzodifuran (BDF),
tetrathiafulvalene (TTF), triphenylamine (TPA), and acceptors including 2,1,3-
benzothiadiazole (BTD), perylene diimide (PDI), tetraazapyrene (TAP) and
dipyrrolylquinoxaline (DPQ) have been investigated. It has been demonstrated that HOMO
and LUMO energy levels and band gaps critically depend on the intrinsic electronic properties
of D and A units as well as the nature of the linker between them. To optimize the electronic
communication between D and A units for potential applications in molecular (opto)electronics,
a variety of π-conjugated ensembles with different D-A architectures have been designed,
synthesized, and characterized in this thesis. Importantly, efficient synthetic approaches to
functionalize the TAP core via halogenation, hydrolysis, oxidation, and condensation have
been developed, allowing the preparation of various kinds of TAP-based D-A molecules. Our
keen interest in such π-conjugates has led us to comprehensively investigate the intramolecular
charge-transfer (ICT) interactions through-bond or through-space between D and A moieties
by UV-Vis-NIR spectroscopy, cyclic voltammetry (CV), transient absorption spectroscopy
(TAS) and density functional theory (DFT) calculations.
Date of Publication
2022
Year of graduation
2022
Theses Type
dissertation
Subject(s)
Language(s)
en
Author(s)
Zhou, Ping |
Faculty/Graduate School
Access(Rights)
open.access
Primary OA Publication
true