The Effect of Intermolecular Hydrogen Bonding on the Fluorescence of a Bimetallic Platinum Complex

The Effect of Intermolecular Hydrogen Bonding on the Fluorescence of a Bimetallic Platinum Complex

The bimetallic platinum complexes are known as unique building blocks and arewidely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. Hence, photophysical study of the bimetallic platinum complexes will be very helpful for the understanding on the opti...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2010-09, Vol.114 (34), p.9007-9013
Main Authors: Zhao, Guang-Jiu, Northrop, Brian H, Han, Ke-Li, Stang, Peter J
Format: Article
Language:eng
Subjects:
A: Dynamics, Clusters, Excited States
Benzophenones - chemistry
Hydrogen Bonding
Organometallic Compounds - chemistry
Platinum - chemistry
Quantum Theory
Solvents - chemistry
Spectrometry, Fluorescence
Thermodynamics
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Summary:The bimetallic platinum complexes are known as unique building blocks and arewidely utilized in the coordination-driven self-assembly of functionalized supramolecular metallacycles. Hence, photophysical study of the bimetallic platinum complexes will be very helpful for the understanding on the optical properties and further applications of coordination-driven self-assembled supramolecular metallacycles. Herein, we report steady-state and time-resolved spectroscopic experiments as well as quantum chemistry calculations to investigate the significant intermolecular hydrogen bonding effects on the intramolecular charge transfer (ICT) fluorescence of a bimetallic platinum compound 4,4′-bis(trans-Pt(PEt3)2OTf)benzophenone 3 in solution. We demonstrated that the fluorescent state of compound 3 can be assigned as a metal-to-ligand charge transfer (MLCT) state. Moreover, it was observed that the formation of intermolecular hydrogen bonds can effectively lengthen the fluorescence lifetime of 3 in alcoholic solvents compared with that in hexane solvent. At the same time, the electronically excited states of 3 in solution are definitely changed by intermolecular hydrogen bonding interactions. As a consequence, we propose a new fluorescence modulation mechanism by hydrogen bonding to explain different fluorescence emissions of 3 in hydrogen-bonding solvents and nonhydrogen-bonding solvents.
ISSN:1089-5639
1520-5215