Geary Elaine A M, McCall Keri L, Turner Andrew, Murray Paul R, McInnes Eric J L, Jack Lorna A, Yellowlees Lesley J, Robertson Neil
School of Chemistry, University of Edinburgh, King's Buildings, Edinburgh, UK EH9 3JJ.
Dalton Trans. 2008 Jul 28(28):3701-8. doi: 10.1039/b719789f. Epub 2008 May 29.
A series of [Pt(ii)(diimine)(dithiolate)] complexes of general formula [Pt{X,X'-(CO(2)R)(2)-bpy}(mnt)] (where X = 3, 4 or 5; R = H or Et, bpy = 2,2'-bipyridyl and mnt = maleonitriledithiolate), have been spectroscopically, electrochemically and computationally characterised and compared with the precursors [Pt{X,X'-(CO(2)R)(2)-bpy}Cl(2)] and X,X'-(CO(2)R)(2)-bpy. The study includes cyclic voltammetry, in situ EPR spectroelectrochemical studies of fluid solution and frozen solution samples, UV/Vis/NIR spectroelectrochemistry, hyrid DFT and TD-DFT calculations. The effect of changing the position of the bpy substituents from 3,3' to 4,4' and 5,5' is discussed with reference to electronic changes seen within the different members of the family of molecules. The performance of the mnt complexes in dye-sensitised solar cells has been previously described and the superior performance of [Pt{3,3'-(CO(2)R)(2)-bpy}(mnt)] is now explained in terms of decreased electronic delocalisation through twisting of the bipyridyl ligand as supported by the EPR and computational results.
一系列通式为[Pt{X,X'-(CO₂R)₂-bpy}(mnt)]（其中X = 3、4或5；R = H或Et，bpy = 2,2'-联吡啶，mnt = 马来腈二硫醇盐）的[Pt(ii)(二亚胺)(二硫醇盐)]配合物已通过光谱、电化学和计算方法进行了表征，并与前体[Pt{X,X'-(CO₂R)₂-bpy}Cl₂]和X,X'-(CO₂R)₂-bpy进行了比较。该研究包括循环伏安法、流体溶液和冷冻溶液样品的原位EPR光谱电化学研究、紫外/可见/近红外光谱电化学、混合密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）计算。参照分子家族不同成员中观察到的电子变化，讨论了将联吡啶取代基的位置从3,3'改变为4,4'和5,5'的影响。此前已描述了mnt配合物在染料敏化太阳能电池中的性能，现在根据EPR和计算结果所支持的联吡啶配体扭转导致电子离域减少，来解释[Pt{3,3'-(CO₂R)₂-bpy}(mnt)]的优异性能。
