Multicomponent Self‐Assembly of Metallo‐Supramolecular Macrocycles and Cages through Dynamic Heteroleptic Terpyridine Complexation

• Published in: Chemistry : a European journal Vol. 24; no. 37; pp. 9274 - 9284
• Main Authors: Wang, Shih‐Yu, Huang, Jyun‐Yang, Liang, Yen‐Peng, He, Yun‐Jui, Chen, Yu‐Sheng, Zhan, Yi‐Yang, Hiraoka, Shuichi, Liu, Yi‐Hung, Peng, Shie‐Ming, Chan, Yi‐Tsu
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 02.07.2018
• Subjects: Assembly; Cadmium; Cages; Chemistry; Complexation; Construction; coordination modes; Lability; Ligands; Metal ions; metalation; Metallography; multicomponent reactions; Parallelograms; Photoluminescence; Photons; self-assembly; Shape recognition; supramolecular chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201801753

Spontaneous formation of the heteroleptic cadmium(II) bis(terpyridine) complex under ambient conditions can be achieved by a combination of 6,6′′‐di(2,6‐dimethoxylphenyl)‐substituted and unsubstituted terpyridine‐based ligands. Building on this dynamic heteroleptic complexation, diverse metallo‐supramolecular macrocycles and cages were readily assembled in quantitative yields from the predesigned multicomponent systems. The complementary ligation reinforced self‐recognition to facilitate the shape‐dependent self‐sorting of a four‐component dynamic library into two well‐defined parallelograms. In addition, the subtle lability difference between homoleptic and heteroleptic complexes led to the site‐selective CdII–ZnII transmetalation in the Sierpiński triangle. Facile construction of a dodecanuclear tetrahedral metallocage was also realized by using two self‐recognizable tritopic building blocks. The photophysical study of the metallo‐supramolecules assembled from the d10 metal ions revealed intense ligand‐based photoluminescence in solution. The self‐assembly strategy described here provides an efficient methodology for building pre‐programmable, sophisticated supramolecular architectures furnished with photoactivity. Complementary ligand pairing: The predesigned dynamic heteroleptic terpyridine complexation leads to facile construction of various multicomponent 2D and 3D metallo‐supramolecules, and enables the shape‐dependent self‐sorting of a four‐component system as well as the site‐selective transmetalation within a structurally preserved assembly (see figure).