6533b7d9fe1ef96bd126cc22

RESEARCH PRODUCT

Humidity-Driven Reversible Transformation and Guest Inclusion in a Two-Dimensional Coordination Framework Tailored by Organic Polyamine Cation

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Using a polyamine cation tetrenH55+ (tetren = tetraethylenepentaamine), we tailored the dynamic layered material (tetrenH5)1.6{CoII(H2O)2[MIV(CN)8]}4·xH2O (1, M = W, x = 12; 2, M = Mo, x = 11.2). 1 and 2 consist of strongly corrugated two-dimensional (2D) cyano-bridged monolayers {CoII(H2O)2[MIV(CN)8]}n2n– of square grid topology stacked in an alternate manner with cationic layers of tetrenH55+ and H2O molecules. The observed single-crystal-to-single-crystal (SCSC) transformation is due to the reversible dehydration of 1 and 2 to the respective monocrystalline materials (tetrenH5)1.6{CoII[MIV(CN)8]}4 (1deh and 2deh). Structural modifications consist of the change of coordination number (C.N.) of Co(II) from 6 to 4 and a degree of corrugation of the coordination skeleton resulting in changes of orthorhombic cell dimensions. The exposition of 1deh to vapors of H2O, MeOH, HCONH2, and MeCN gives 1reh, 1deh·5.6MeOH, 1deh·4HCONH2, and 1deh·2.4MeCN phases, respectively. 1reh reveals structural, physical, and phy...