Pei Xiao-Li, Guan Zong-Jie, Nan Zi-Ang, Wang Quan-Ming
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing, 100084, P. R. China.
Angew Chem Int Ed Engl. 2021 Jun 21;60(26):14381-14384. doi: 10.1002/anie.202104391. Epub 2021 May 20.
Acetelyenediide (C ) species have been encapsulated in bimetallic and trimetallic clusters: (AuL) Ag (C≡C) (2) and (AuL) AgCu (C≡C) (3), L=phenylbis(2-pyridyl)phosphine (PPhpy ). Single-crystal X-ray diffraction analysis revealed that they are isostructural and six silver atoms in 2 are replaced with copper in 3. Both clusters have a trefoil skeleton, which can be viewed as three trigonal bipyramidal (LAu-C≡C-AuL)M Ag (M=Ag/Cu) motifs sharing a common silver atom. TDDFT calculations showed Cu-doping significantly increases the energy level of (C -Cu)-involved occupied orbital, thus inducing interesting transition coupling of dual-emission at low temperature. This work not only provides a strategy for constructing heterometallic clusters, but also shows the prospect for pursuing novel thermochromic luminescent materials by incorporating multi-congeneric metal components.
乙炔二亚胺（C ）物种已被封装在双金属和三金属簇中：(AuL)₂Ag₂(C≡C)₂₂(2) 和 (AuL)₂AgCu(C≡C)₂₂(3)，L = 苯基双(2 - 吡啶基)膦 (PPhpy₂)。单晶X射线衍射分析表明它们是同构的，并且2中的六个银原子在3中被铜取代。两个簇都具有三叶骨架，可视为三个三角双锥 (LAu - C≡C - AuL)M₂Ag (M = Ag/Cu) 基序共享一个共同的银原子。TDDFT计算表明，铜掺杂显著提高了涉及 (C - Cu) 的占据轨道的能级，从而在低温下诱导出有趣的双发射跃迁耦合。这项工作不仅提供了一种构建异金属簇的策略，还展示了通过引入多同属金属组分来追求新型热致变色发光材料的前景。
