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三线态圆偏振发光活性螺旋烯-二硫纶铂联吡啶配合物

Triplet state CPL active helicene-dithiolene platinum bipyridine complexes.

作者信息

Biet Thomas, Cauchy Thomas, Sun Qinchao, Ding Jie, Hauser Andreas, Oulevey Patric, Bürgi Thomas, Jacquemin Denis, Vanthuyne Nicolas, Crassous Jeanne, Avarvari Narcis

机构信息

Laboratoire Moltech-Anjou, Université d'Angers, CNRS UMR 6200, 2 bd Lavoisier, 49045 Angers, France.

Department of Physical Chemistry, University of Geneva, 30 Quai Ernest Ansermet, CH-1211 Geneva, Switzerland.

出版信息

Chem Commun (Camb). 2017 Aug 25;53(66):9210-9213. doi: 10.1039/c7cc05198k. Epub 2017 Aug 2.

DOI:10.1039/c7cc05198k
PMID:28766593
Abstract

Chiral metal dithiolene complexes represent a family of chiral precursors, which can give rise to molecular materials with properties resulting from the interplay of chirality with conductivity, magnetism, and photophysics. We describe herein the first examples of chiral metal diimine dithiolene complexes, by the use of a platinum(ii) centre coordinated by 2,2'-bipyridine and helicene-dithiolene ligands. The straightforward synthesis of racemic and enantiopure complexes allows the preparation of luminescent Pt(bipy) [4] and [6]helicene compounds for which the solid-state structure was determined as well. TD-DFT calculations support the assignment of the low-energy bands observed in the UV-vis absorption spectra as mixed metal-ligand-to-ligand charge transfer transitions and confirm that the emission band results from the T excited state. Interestingly, the enantiopure [6]helicene complexes show CPL activity at room temperature in acetonitrile solutions with an anisotropy factor of 3 × 10.

摘要

手性金属二硫纶配合物是一类手性前体,它们能够产生具有手性与导电性、磁性和光物理相互作用所导致性质的分子材料。我们在此描述了手性金属二亚胺二硫纶配合物的首个实例,其通过使用由2,2'-联吡啶和螺旋烯二硫纶配体配位的铂(II)中心来实现。外消旋和对映体纯配合物的直接合成使得制备出了发光的Pt(bipy)[4]和[6]螺旋烯化合物,并且还确定了它们的固态结构。TD-DFT计算支持将紫外可见吸收光谱中观察到的低能带归属为混合的金属-配体-配体电荷转移跃迁,并证实发射带源于T激发态。有趣的是,对映体纯的[6]螺旋烯配合物在室温下于乙腈溶液中表现出圆偏振发光活性,其各向异性因子为3×10。

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