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A Strong Donor–Acceptor System Based on a Metal Chalcogenide Cluster and Porphyrin
journal contribution
posted on 2017-06-27, 14:52 authored by Jing Xu, Li-Jun Xue, Jin-Le Hou, Zhong-Nan Yin, Xuan Zhang, Qin-Yu Zhu, Jie DaiAlthough great progress
has been made for charge transfer (CT) compounds of various organic
donor–acceptor systems, no CT compounds containing both inorganic
chalcogenide cluster anions and organic porphyrin cations have been
reported. Herein, a germanium chalcogenide cluster (Ge4S104–) is chosen as an electron donor
and a methylated tetrakis(4-pyridyl)porphyrin (5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin, TMPyP) is selected as an electron
acceptor to create chalcogenide cluster–porphyrin CT compounds
(TMPyP-Ge4S10)·5H2O (1) and (MnTMPyP-Ge4S10)·13H2O (2). Their crystal structures have been characterized
by single-crystal X-ray diffraction. Compound 1 is an
ionic CT salt assembled through interion interactions, and compound 2 is a neutral CT dyad formed by metal–ligand axial
coordination of the chalcogenide cluster with manganese porphyrin.
The strong charge transfer properties are revealed by electronic spectra,
theoretical calculations, 1H NMR, and ESR. The CT intensity
of the chalcogenide cluster–porphyrin system can be modulated
by metalation. The fluorescence and photocurrent response properties
of 1 and 2 are related to the CT intensity.