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Linking Bridged Tetracopper Complexes with Neutral Dipyridyl Compounds to Coordination Polymers and Discrete Metalacages
Author(s) -
Shiu LerChun,
Chuang JenHan,
Wu TianShung,
Shiu KomBei
Publication year - 2017
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201600847
Subject(s) - chemistry , supramolecular chemistry , density functional theory , crystallography , polymer , coordination polymer , bipyridine , stereochemistry , medicinal chemistry , crystal structure , computational chemistry , organic chemistry
The bridged tetracopper(I) complex [{Cu 2 (μ‐dppm) 2 } 2 (μ‐(1,3‐ O 2 CC 6 H 4 ( CO 2 ) 2 )]( BF 4 ) 2 ( 2 ( BF 4 ) 2 ) was prepared. This complex and the neutral dipyridyl compounds ( NN ; NN = 4,4′‐bipyridine (bpy), 1,2‐bis(4‐pyridyl)ethane (bpa), 4,4′‐trimethylenedipyridine (tmp)) can form dynamic equilibria in CH 2 Cl 2 . From the equilibrium mixtures containing 2 ( BF 4 ) 2 and NN with 2 ( BF 4 ) 2 / NN = 1:1, different supramolecular compounds were obtained as single crystals, and their structure were determined by X‐ray crystallography. The flexibility of NN is found to be important in determining the outcome of the reactions with a rigid bpy, leading to the formation of the coordination polymer [{Cu 2 (μ‐dppm) 2 } 2 (μ‐1,3‐ C 6 H 4 ( CO 2 ) 2 )(μ‐bpy)] n ( BF 4 ) 2 n ( 3 ( BF 4 ) 2 n ), whereas with flexible bpa and tmp direct the formation of the metalacages [{Cu 2 (μ‐dppm) 2 } 2 (μ‐1,3‐ C 6 H 4 ( CO 2 ) 2 )(μ‐ NN )]( BF 4 ) 2 ( NN = bpa, 4 ( BF 4 ) 2 ; tmp, 5 ( BF 4 ) 2 ), respectively, as supported by density functional theory ( DFT ) calculation results.