Department of Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology , 2-12-1-NE1 O-okayama, Meguro-ku, Tokyo 152-8550, Japan.
J Am Chem Soc. 2013 Sep 11;135(36):13266-9. doi: 10.1021/ja406144h. Epub 2013 Aug 27.
We synthesized for the first time a series of emissive ring-shaped Re(I) complexes (Re-rings) with various numbers of Re(I) units and various lengths of bridge ligands. The photophysical properties of the Re-rings could be varied widely through changes in the size of the central cavity. A smaller central cavity of the Re-rings induced intramolecular π-π interactions between the ligands and consequently caused a stronger emission and a longer lifetime of the excited state. The Re-rings can function as efficient and durable photosensitizers. The combination of a trinuclear Re-ring photosensitizer with fac-Re(bpy)(CO)3(MeCN) (bpy = 2,2'-bipyridine) as a catalyst photocatalyzed CO2 reduction with the highest quantum yield of 82%.
我们首次合成了一系列具有不同数量的 Re(I) 单元和不同长度桥联配体的发射性环形 Re(I) 配合物（Re 环）。通过改变中心腔的大小，可以广泛改变 Re 环的光物理性质。较小的 Re 环中心腔诱导配体之间的分子内π-π相互作用，从而导致更强的发射和更长的激发态寿命。Re 环可以作为高效和持久的光敏剂。将三核 Re 环光敏剂与 fac-[Re(bpy)(CO)3(MeCN)] +（bpy = 2,2'-联吡啶）作为催化剂结合起来，可实现 CO2 还原，量子产率高达 82%。
