Conjugated-Linker Dependence Of The Photophysical Properties And Electronic Structure Of Chlorin Dyads

JOURNAL OF PORPHYRINS AND PHTHALOCYANINES(2021)

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摘要
The synthesis, photophysical properties and electronic structure of seven new chlorin dyads and associated benchmark monomers are described. Each dyad contains two identical chlorins linked at the macrocycle beta-pyrrole 13-position. The extent of electronic communication between chlorin constituents depends on the nature of the conjugated linker. The communication is assessed by modification of prominent ground-state absorption and redox properties, rate constants and yields of excited-state decay processes, and molecular-orbital characteristics. Relative to the benchmark monomers, the chlorin dyads in toluene exhibit a substantial bathochromic shift of the long-wavelength absorption band (30 nm average), two-fold increased radiative rate constant [average (10 ns)(-1) vs. (22 ns)(-1)], reduced singlet excited-state lifetimes (average 5.0 ns vs. 8.2 ns), and increased fluorescence quantum yields (average 0.56 vs. 0.42). The excited-state lifetime and fluorescence yield for the chlorin dyad with a benzothiadiazole linker are reduced substantially in benzonitrile vs. toluene due largely to similar to 25-fold accelerated internal conversion. The results aid design strategies for molecular architectures that may find utility in solar-energy conversion and photomedicine.Electronic communication between strongly-coupled chlorins in dyads is highly dependent upon the nature and attachment sites of the conjugated linker. The extent of communication is manifested in ground-state absorption and redox properties, rate constants and yields of excited-state decay processes, and molecular-orbital characteristics.
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关键词
chlorin dyads, conjugated linkers, orbital splitting, electronic communication, excited-state dynamics
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