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Reversible Crystal Transformations and Luminescence Vapochromism by Fast Guest Exchange in Cu(I) Coordination
Hyunjin Park1, Eunjin Kwon1, Hojae Chiang1
1Department of Chemistry (BK21 plus) and Research Institute of Natural Science, Gyeongsang National University , Jinju 52828, Korea.
Abstract:
Six Cu(I) coordination polymers (CPs)-[Cu2I2L2]n (1), {[Cu2I2L2]·2MeCN}n (2), [Cu4I4L2]n (3), {[Cu4I4L2]·CH2Cl2}n (4), {[Cu4I4L2]·CHCl3}n (5), and {[Cu4I4L2]·C6H6}n (6)-were synthesized by self-assembly reactions of CuI and the flexible mixed N/S donor ligand 4-(2-(cyclohexylthio)ethoxy)pyridine (L). Single-crystal X-ray diffraction analyses reveal that these 1D CPs form sets of supramolecular isomers; 1 and 2 are based on Cu2I2 rhomboids, while 3-6 are based on cubane Cu4I4 clusters. Crystal-to-crystal transformations of CPs 1-6 were reversible under heat or in an appropriate solvent (acetonitrile, dichloromethane, chloroform, or benzene). In addition, crystal transformations between CPs 1 and 3 occurred through addition of L or CuI. Moreover, CPs 3-6 exhibited reversible guest exchange and crystal transformations on exposure to the vapor of volatile organic compounds and heat. Remarkably, a guest molecule was exchanged by other guest molecules in the vapor phase within very short times and without the use of acetonitrile as a solvent, which normally plays a key role in trapped solvent exchange experiments.
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