Facile Tuning of Luminescent Platinum(II) Schiff Base Complexes from Yellow to Near-Infrared: Photophysics, Electrochemistry, Electrochemiluminescence and Theoretical Calculations

被引:30
|
作者
Reid, Ellen F. [1 ]
Cook, Vernon C. [2 ]
Wilson, David J. D. [1 ]
Hogan, Conor F. [1 ]
机构
[1] La Trobe Univ, Dept Chem, La Trobe Inst Mol Sci, Melbourne, Vic 3086, Australia
[2] CSIRO, Mol Hlth Technol, Clayton, Vic 3168, Australia
基金
澳大利亚研究理事会;
关键词
density functional theory; electrochemiluminescence; electrochemistry; luminescence; platinum Schiff base complexes; EFFICIENT ELECTROGENERATED CHEMILUMINESCENCE; BASIS-SETS; IRIDIUM(III) COMPLEXES; SELECTIVE EXCITATION; HIGHLY EFFICIENT; EMISSION; PHOTOLUMINESCENCE; DERIVATIVES; MONOMERS; SYSTEMS;
D O I
10.1002/chem.201302339
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The photophysical and related properties of platinum(II) Schiff base complexes can be finely and predictably tuned over a wide range of wavelengths by small and easily implemented changes to ligand structure. A series of such complexes, differing only in the number and positioning of methoxy substituents on the phenoxy ring, were synthesised and their photophysical, electrochemical and electrochemiluminescent (ECL) properties investigated. Theoretical calculations were performed in order to gain further insight into the relationship between structure and properties in these materials. By positioning methoxy groups para and/or ortho to either the imine or the oxygen group on the ligand, electron density could be directed selectively toward the LUMO or HOMO as required. This allowed the emission colour (both photoluminescent and electrochemiluminescent) to be tuned over a wide range between 587 and 739nm. The variation in orbital energies was also manifested in the positions of the absorption bands and the redox properties of the complexes, as well as in the NMR shifts for the uncoordinated ligands. All reported complexes displayed intense electrochemiluminescence (ECL), which could be initiated either by annihilation or co-reactant pathways. The relationship between the electrochemical and photophysical properties and the efficiency of the ECL is discussed. For two of the complexes solid-state ECL could be generated from electrodeposited layers of the complex.
引用
收藏
页码:15907 / 15917
页数:11
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