Abstract
Our recent achievements relating to photofunctional molecules are addressed. Section 1 discloses a new concept of photoisomerization. Pyridylpyrimidine-copper complexes undergo a ring inversion that can be modulated by the redox state of the copper center. In combination with an intermolecular photoelectron transfer (PET) initiated by the metal-to-ligand charge transfer (MLCT) transition of the Cu(I) state, we realize photonic regulation of the ring inversion. Section 2 reports on the first examples of heteroleptic bis(dipyrrinato)zinc(II) complexes. Conventional homoleptic bis(dipyrrinato)zinc(II) complexes suffered from low fluorescence quantum yields, whereas the heteroleptic ones feature bright fluorescence even in polar solvents. Section 3 describes our new findings on Pechmann dye, which was first synthesized in 1882. New synthetic procedures for Pechmann dye using dimethyl bis(arylethynyl)fumarate as a starting material gives rise to its new structural isomer. We also demonstrate potentiality of a donor-acceptor-donor type of Pechmann dye in organic electronics.
Highlights
Redox switching in the CuII/CuI complex is accompanied by a change in the coordination environment [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15]
The i-CuII generated in the course of the photoelectron transfer (PET) isomerized to o-CuII for two reasons: (i) the pyrimidine ring rotation in the CuII state was not frozen at 203 K, and (ii) i-CuII was thermodynamically unfavorable, because of the steric repulsion
A key feature of the present system is that the population of bistable isomers, i-Cu and o-Cu, possessing different redox potentials ( E0' = 0.14 V), is reversibly converted by light and heat stimuli through a PET process with
Summary
Pechmann Dye, E-5,5'-diphenylbifuranylidenedione (P55-Ph, Scheme 2a), was first reported by von Pechmann and coworkers in 1882 [97] This series of molecules possesses good photochemical properties, including an intense absorption at approximately 550 nm, which is ascribed to a 1 - *. (a) Pechmann dye (P55-Ph) and its structural isomers (P66-Ph, P56-Ph, and P55’Ph, and (b) representative synthetic route for P55-Ph and P66-Ph. Recently, D-A-D and A-D-A (D: donor, A: acceptor) quadrupolar types of molecules have attracted the attention of chemists. D-A-D and A-D-A (D: donor, A: acceptor) quadrupolar types of molecules have attracted the attention of chemists These types of molecules feature intense one-photon absorptions in the visible and NIR regions, which are due to intramolecular charge-transfer (ICT) transitions, high fluorescent quantum yields, and large two-photon absorption cross sections. Plausible reaction mechanism for the generation of P55-5, P66-5, and P56-5 from E-5
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