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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes: Fundamental switching of the nature of S _1 and T _1 states from MLCT to MC
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Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes: Fundamental switching of the nature of S _1 and T _1 states from MLCT to MC

机译：钌4,4'-双-1,2,3-三唑基配合物的合成，表征和理论研究：S _1和T _1状态性质从MLCT到MC的根本转换

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摘要

The series of complexes [Ru(bpy) _(3-n)(btz) _n][PF _6] _2 (bpy = 2,2′-bipyridyl, btz = 1,1′-dibenzyl-4,4′-bi-1,2,3-triazolyl, 2n = 1, 3n = 2, 4n = 3) have been prepared and characterised, and the photophysical and electronic effects imparted by the btz ligand were investigated. Complexes 2 and 3 exhibit MLCT absorption bands at 425 and 446 nm respectively showing a progressive blue-shift in the absorption on increasing the btz ligand content when compared to [Ru(bpy) _3][Cl] _2 (1). Complex 4 exhibits a heavily blue-shifted absorption spectrum with respect to those of 1-3, indicating that the LUMO of the latter are bpy-centred with little or no btz contribution whereas that of 4 is necessarily btz-centred. DFT calculations on analogous complexes 1′-4′ (in which the benzyl substituents are replaced by methyl) show that the HOMO-LUMO gap increases by 0.3 eV from 1′-3′ through destabilisation of the LUMO with respect to the HOMO. The HOMO-LUMO gap of 4′ increases by 0.98 eV compared to that of 3′ due to significant destabilisation of the LUMO. Examination of TDDFT data show that the S _1 states of 1′-3′ are 1MLCT in character whereas that of 4′ is ~1MC. The optimisation of the T _1 state of 4′ leads to the elongation of two mutually trans Ru-N bonds to yield [Ru(κ ~2-btz)(κ ~1-btz) _2] ~(2+), confirming the ~3MC character. Thus, replacement of bpy by btz leads to a fundamental change in the ordering of excited states such that the nature of the lowest energy excited state changes from MLCT in nature to MC.
机译：络合物系列[Ru（bpy）_（3-n）（btz）_n] [PF _6] _2（bpy = 2,2'-联吡啶，btz = 1,1'-二苄基-4,4'-bi已制备并表征了1,1,2,3-三唑基（2n = 1，3n = 2，4n = 3），并研究了btz配体赋予的光物理和电子效应。与[Ru（bpy）_3] [Cl] _2（1）相比，配合物2和3在425和446 nm处分别表现出MLCT吸收带，随着btz配体含量的增加，吸收呈现渐进的蓝移。配合物4的吸收光谱相对于1-3的吸收光谱显示出严重的蓝移，表明后者的LUMO以bpy为中心，几乎没有btz贡献，而4的LUMO则必须以btz为中心。对类似络合物1'-4'（其中苄基取代基被甲基取代）的DFT计算表明，由于LUMO相对于HOMO不稳定，HOMO-LUMO间隙从1'-3'增加了0.3 eV。与3'相比，4'的HOMO-LUMO间隙增加了0.98 eV，这是因为LUMO的显着不稳定。 TDDFT数据的检查表明，1'-3'的S _1状态为1MLCT，而4'的S _1状态为〜1MC。 4'的T _1状态的优化导致两个相互反式的Ru-N键的延伸，从而产生[Ru（κ〜2-btz）（κ〜1-btz）_2]〜（2+），从而证实了〜3MC字符。因此，用btz替代bpy会导致激发态顺序的根本变化，从而使最低能量激发态的性质从MLCT变为MC。

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