Savchuk Mariia, Vertueux Steven, Cauchy Thomas, Loumaigne Matthieu, Zinna Francesco, Di Bari Lorenzo, Zigon Nicolas, Avarvari Narcis
Univ Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, France.
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via G. Moruzzi, 13, 56124, Pisa, Italy.
Dalton Trans. 2021 Aug 4;50(30):10533-10539. doi: 10.1039/d1dt01752g.
The controlled preparation of chiral emissive transition metal complexes is fundamental in the field of circularly polarized luminescence (CPL) active molecular materials. For this purpose, enantiopure Zn(ii) complexes 1 and 2 based on a tetradentate salen ligand surrounded by [4]helicene moieties, together with their racemic counterpart 3, have been herein synthesized. Chirality is primarily brought about by chiral 1,2-cyclohexane-diamines. Alternatively, achiral complex 4 based on ortho-phenylene-diamine has been prepared as well. Single crystal X-ray diffraction analyses have been performed on helicenic intermediates 8 and 9 and complexes 1 and 4. Complexes 1 and 4 display the typical tetradentate O,N,N,O coordination around Zn(ii) characteristic of salen ligands, and bear two [4]helicene moieties. The zinc complexes are luminescent in the visible range around 560 nm at room temperature in aerated solutions with the QY reaching ca. 15% for a luminescence lifetime of 5.5 ns. The optical activities of these complexes have been assessed by CD and CPL, and compared to DFT calculations.
手性发光过渡金属配合物的可控制备是圆偏振发光（CPL）活性分子材料领域的基础。为此，本文合成了基于由[4]螺旋烯部分包围的四齿salen配体的对映体纯Zn（II）配合物1和2，以及它们的外消旋对应物3。手性主要由手性1,2 - 环己二胺引起。另外，还制备了基于邻苯二胺的非手性配合物4。对螺旋烯中间体8和9以及配合物1和4进行了单晶X射线衍射分析。配合物1和4在Zn（II）周围显示出salen配体典型的四齿O，N，N，O配位，并带有两个[4]螺旋烯部分。锌配合物在室温下于通气溶液中在560 nm左右的可见光范围内发光，量子产率约为15%，发光寿命为5.5 ns。通过圆二色性（CD）和圆偏振发光（CPL）评估了这些配合物的光学活性，并与密度泛函理论（DFT）计算结果进行了比较。
