Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 14, Pages 6136-6142Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c00245
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Funding
- European Research Council [695009]
- UK Engineering and Physical Sciences Research Council (EPSRC) [EP/T031603/1, EP/P027067/1]
- Deutsche Forschungsgemeinschaft (DFG)
- Cambridge Trust
- Chinese Scholarship Council (CSC)
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This study found that the solvent environment plays a crucial role in determining the chirality of coordination cages formed during self-assembly, with the handedness of the metal centers being dependent on the solvent. Further analysis revealed that the Delta configuration is entropically favored but enthalpically disfavored.
An enantiopure ligand with four bidentate metal-binding sites and four (S)-carbon stereocenters self-assembles withoctahedral ZnIIor CoIIto produceO-symmetric M8L6coordination cages. The Lambda-or Delta-handedness of the metal centers forming thecorners of these cages is determined by the solvent environment: the same (S)-ligand produces one diastereomer, (S)24-Lambda 8-M8L6,inacetonitrile but another with opposite metal-center handedness, (S)24-Delta 8-M8L6, in nitromethane. Van'tHoffanalysis revealed the Delta stereochemical configuration to be entropically favored but enthalpically disfavored, consistent with a loosening of the coordinationsphere and an increase in conformational freedom following Lambda-to-Delta transition. The binding of 4,4 '-dipyridyl naphthalenediimideand tetrapyridyl Zn-porphyrin guests did not interfere with the solvent-driven stereoselectivity of self-assembly, suggestingapplications where either a Lambda-or Delta-handed framework may enable chiral separations or catalysis
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