From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built Upon Bis(benzylthio)alkanes (BzS(CH2 )n SBz; n = 1-9)

Inorganic Chemistry
Adrien SchlachterMichael Knorr

Abstract

With the objective to establish a correlation between the spacer distance and halide dependence on the structural features of coordination polymers (CPs) assembled by the reaction between CuX salts (X = Cl, Br, I) and dithioether ligands BzS(CH2) n SBz (n = 1-9; Bz = benzyl), a series of 26 compounds have been prepared and structurally investigated. A particular attention has been devoted to the design of networks with extremely long and flexible methylene spacer units between the SBz donor sites. Under identical conditions, CuI and CuBr react with BzSCH2Bz (L1) affording respectively the one-dimensional (1D) CPs {Cu(μ2-I)2Cu}(μ-L1)2] n (CP1) and {Cu(μ2-Br)2Cu}(μ-L1)2] (CP2), which incorporate Cu(μ2-X)2Cu rhomboids as secondary building units (SBUs). The hitherto unknown architecture of two-dimensional (2D) layers obtained with CuCl (CP3) differs from that of CP1 and CP2, which bear inorganic -Cl-Cu-Cl-Cu-Cl- chains interconnected through bridging L1 ligands, thus forming a 2D architecture. The crystallographic characterization of a 1D CP obtained by reacting CuI with 1,3-bis(benzylthio)propane (L2) reveals that [{Cu(μ2-I)2Cu}(μ-L2)2] n (CP4) contains conventional Cu2I2 rhomboids as SBUs. In contrast, unusual isostructural CP...Continue Reading

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