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Synthesis and Properties of Fused‐Ring‐Expanded Porphyrins that were Core‐Modified with Group 16 Heteroatoms
Author(s) -
Xu HaiJun,
Mack John,
Wu Di,
Xue ZhaoLi,
Descalzo Ana B.,
Rurack Knut,
Kobayashi Nagao,
Shen Zhen
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200956
Subject(s) - heteroatom , thiophene , ring (chemistry) , helicene , chemistry , chalcogen , crystallography , fluorescence , porphyrin , intersystem crossing , photochemistry , sulfur , molecule , organic chemistry , physics , nuclear physics , singlet state , excited state , quantum mechanics
The synthesis of a series of novel core‐modified and fused‐ring‐expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem‐crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine‐tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso ‐phenyl rings, is also examined.