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首页> 外文期刊>New Journal of Chemistry >Half-lantern cyclometalated Pt(ii) and Pt(iii) complexes with bridging heterocyclic thiolate ligands: synthesis, structural characterization, and electrochemical and photophysical properties
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Half-lantern cyclometalated Pt(ii) and Pt(iii) complexes with bridging heterocyclic thiolate ligands: synthesis, structural characterization, and electrochemical and photophysical properties

机译：具有桥接杂环硫醇酸盐配体的半灯环状的Pt（II）和Pt（III）配合物：合成，结构表征和电化学和光物理性质

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摘要

The half-lantern Pt(ii)-Pt(ii) cyclometalated complexes [{Pt(ppy-C-2,N)(-N<^>S)}(2)] [Hppy = 2-phenylpyridine; HN<^>S = 2-mercaptopyridine (Spy, 1a), 5-(trifluoromethyl)-2-mercaptopyridine (SpyCF(3), 1b), 2-mercaptopyrimidine (SpyN, 1c), 2-mercaptobenzothiazole (SBt, 1d) and 2-mercaptobenzimidazole (SBi, 1e)] were synthesized by reaction of [Pt(ppy-C-2,N)Cl(dmso)] (A) with an ethanolic solution of the corresponding sodium thiolate salts, thus providing a new direct approach to obtain this type of complexes in high yield. 1a, 1d and 1e were previously reported by other routes (see the text). These complexes exhibit intense red emission (QY 13.2-37.4%, CH2Cl2) derived from a triplet metal-metal to ligand charge transfer ((MMLCT)-M-3) excited state both in CH2Cl2 solution and in the solid state (298 and 77 K), consistent with strong PtPt interactions. The electrochemical behavior of these complexes was examined to get insight into the influence of the bridging ligand on the metallointeractions. By stirring compounds 1a-c in CHCl3, two electron oxidized diplatinum(iii) derivatives [{Pt(ppy-C-2,N)(-N<^>S)Cl}(2)] (2a-c) were successfully obtained (2a previously reported by Kato et al.). The X-ray structure of 2cCHCl(3) confirmed the retention of the half-lantern structure for the Pt(iii)-Pt(iii) dichloro complex and a shortening of the Pt-Pt distance in relation to 1.
机译：半灯笼的Pt（II）-Pt（ⅱ）环金属配合物[{铂（PPY-C-2，N）（ - N的<^> S）} ...（2）] [Hppy = 2-苯基吡啶; HN <^> S = 2-巯基吡啶（间谍，1A），5-（三氟甲基）-2-巯基吡啶（SpyCF（3），图1b），2-巯基嘧啶（SpyN，1C），2-巯基苯（SBT，1d）的和2-巯基苯并咪唑（SBI，1E）]通过的[PT（PPY-C-2，N）氯（DMSO）]（A）与相应的钠的乙醇溶液硫醇盐，从而提供了一种新的直接反应来合成接近，以获得高收率这种类型的络合物。参照图1A，1D和1E进行了先前通过其它途径报道（见文本）。这些配合物显示出强烈的红色发光（QY 13.2-37.4％，二氯甲烷）从三重金属 - 金属衍生的配体电荷转移（（MMLCT）-M-3）激发态都在CH2Cl2溶液和在固体状态（298和77 K），具有很强的互动PTPT一致。检查这些复合物的电化学行为，深入了解在metallointeractions桥接配体的影响。通过在CHCl 3中搅拌化合物1A-1C，两个电子氧化二铂（III）的衍生物[{铂（PPY-C-2，N）（ - N的<^> S）氯}（2）]（2A-C）被成功获得的（图2a先前由Kato等人的报道。）。 2cCHCl的（3）的X射线结构证实了半灯笼结构的Pt组成的保留（ⅲ）-Pt（ⅲ）二氯络合物和铂的Pt距离相对于1缩短。

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