Abstract
A new mixed-valence Cu(I)–Cu(II) 1D coordination polymer, [CuI4CuIIBr4(Cy2dtc)2]n, with an infinite chain structure is synthesized by the reaction of Cu(Cy2dtc)2 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2) with CuBr·S(CH3)2. The as-synthesized polymer consists of mononuclear copper(II) units of CuII(Cy2dtc)2 and tetranuclear copper(I) cluster units, CuI4Br4. In the cluster unit, all the CuI ions have distorted trigonal pyramidal coordination geometries, and the CuI–CuI or CuI–CuII distances between the nearest copper ions are shorter than the sum of van der Waals radii for Cu–Cu.
Highlights
IntroductionCrystal engineering of coordination polymers attracts increased attention in the field of materials science because of their exceptional chemical and physical properties, such as magnetic [1–3] and conductive [4–17], dielectric [18–20], gas-absorbing [21–23], and catalytic properties [24–27]
Crystal engineering of coordination polymers attracts increased attention in the field of materials science because of their exceptional chemical and physical properties, such as magnetic [1–3] and conductive [4–17], dielectric [18–20], gas-absorbing [21–23], and catalytic properties [24–27].In particular, mixed-valence coordination polymers have attracted considerable interest as a new class of functional materials because of their unique infinite structures and electronic states formed by the combination of different metal ions having versatile coordination architectures and a variety of organic bridging ligands
Complex 1 was synthesized as black single crystals by the reaction of the acetonitrile/acetone solution of CuBr·S(CH3)[2] with the CHCl3 solution of Cu(Cy2dtc)[2] at room temperature (Scheme 1)
Summary
Crystal engineering of coordination polymers attracts increased attention in the field of materials science because of their exceptional chemical and physical properties, such as magnetic [1–3] and conductive [4–17], dielectric [18–20], gas-absorbing [21–23], and catalytic properties [24–27]. Mixed-valence coordination polymers have attracted considerable interest as a new class of functional materials because of their unique infinite structures and electronic states formed by the combination of different metal ions having versatile coordination architectures and a variety of organic bridging ligands. Dithiocarbamate (DTC) derivatives are excellent candidates for use as ligands in mixed-valence coordination polymers [12–17,28] because of their ability to bridge metal ions via sulfur atoms, which have large atomic orbitals [29]. We focused on the synthesis of novel coordination polymers, based on DTC derivatives, with the subsequent elucidation of their carrier transport properties. We successfully synthesized a new mixed-valence coordination polymer with a DTC ligand, [CuI4CuIIBr4(Cy2dtc)2]n 1 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2), and investigated its crystal structure and electroconducting properties
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