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Coordination‐Driven Selective Formation of D 2 Symmetric Octanuclear Organometallic Cages
Author(s) -
Zhang Long,
Lin YueJian,
Li ZhenHua,
Fraser Stoddart J.,
Jin GuoXin
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101204
Subject(s) - supramolecular chemistry , iridium , rhodium , chemistry , chelation , selectivity , group 2 organometallic chemistry , organometallic chemistry , metal , coordination complex , stereochemistry , crystallography , combinatorial chemistry , molecule , catalysis , inorganic chemistry , crystal structure , organic chemistry
The coordination‐driven self‐assembly of organometallic half‐sandwich iridium(III)‐ and rhodium(III)‐based building blocks with asymmetric ambidentate pyridyl‐carboxylate ligands is described. Despite the potential for obtaining a statistical mixture of multiple products, D 2 symmetric octanuclear cages were formed selectively by taking advantage of the electronic effects emanating from the two types of chelating sites – ( O , O’ ) and ( N , N’ ) – on the tetranuclear building blocks. The metal sources and the lengths of bridging ligands influence the selectivity of the self‐assembly. Experimental observations, supported by computational studies, suggest that the D 2 symmetric cages are the thermodynamically favored products. Overall, the results underline the importance of electronic effects on the selectivity of coordination‐driven self‐assembly, and demonstrate that asymmetric ambidentate ligands can be used to control the design of discrete supramolecular coordination complexes.