Synthesis of microporous coordination polymers by in situ terminal alkyne coupling reactions

INOR 664

Shuangbing Han, Shuangbing_Han@brown.edu, Brian Luisi, Brian_Luisi@brown.edu, and Brian Moulton, brian_moulton@brown.edu. Chemistry Department, Brown University, 324 Brook Street, Providence, RI 02912
In situ terminal alkyne coupling reactions were successfully used as a design element to synthesize microporous coordination polymers including 3,3'-(1,3-butadiyne-1,4-diyl)bis-pyridine copper, and 4,4'-(1,3-butadiyne-1,4-diyl)bis-benzoic copper. Longer/larger ligands 3,3'-(1,3-butadiyne-1,4-diyl)bis-pyridine and 4,4'-(1,3-butadiyne-1,4-diyl)bis-benzoate were formed in situ from 3-ethynylpyridine and 4-ethynyl benzoate. The single crystal x-ray structures showed that 3,3'-(1,3-butadiyne-1,4-diyl)bis-pyridine copper contains about 4Å 1D channels and 4,4'-(1,3-butadiyne-1,4-diyl)bis-benzoic copper contains about 12Å 1D channels. This new convergent method can overcome some limitations inherent in the traditional divergent approach, such as solubility and interpenetration.