Xiao-Ping Zhou, Zhengtao Xu,* Matthias Zeller, Allen D. Hunter, Stephen Sin-Yin Chui, and Chi-Ming Che.
Abstract: We report dynamic, multiple single-crystal to single-crystal transformations of a coordination network system based on a semirigid molecule, TCPSB = 1,3,5-tri(40-carboxyphenylsulphonyl)benzene, which nicely balances shape persistence and flexibility to bring about the framework dynamics in the solid state. The networks here generally consist of (1) the persistent core component (denoted as CoTCPSB) of linear CoII aqua clusters (CoOCoO-Co) integrated into 2D grids by 4,40- bipyridine and TCPSB and (2) ancillary ligands (AL) on the two terminal CoII ions—these include DMF (N,N0-dimethylformamide), DMA (N,N0-dimethylacetamide), CH3CN, and water. Most notably, the ancillary ligand sites are highly variable and undergo multiple substitution sequences while maintaining the solid reactants/products as single-crystals amenable to X-ray structure determinations. For example, when immersed in CH3CN, the AL of an as-made single crystal of CoTCPSBDMF (i.e., DMF being the AL) is replaced to form CoTCPSBCH3CN, which, in air, readily loses CH3CN to form CoTCPSBH2O; the CoTCPSBH2O single crystals, when placed in DMF, give back CoTCPSBDMF in single-crystal form. Other selective, dynamic exchanges include the following: CoTCPSBDMF reacts with CH3CN (to form CoTCPSBCH3CN) but NOT with water, methanol, ethanol,DMA, or pyridine; CoTCPSBH2O specifically pick outs DMF from a mixture of DMF, DMA, and DEF; an amorphous, dehydrated solid from CoTCPSBH2O regains crystalline order simply by immersion in DMF (to form CoTCPSBDMF). Further exploration with functional, semirigid ligands like TCPSB shall continue to uncover a wider array of advanced dynamic behaviors in solid state materials.
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ic2007292.pdf
