Construction of Copper(I) Coordination Polymers of 1,2,4,5-Tetracyanobenzene with Zigzag Sheet and Porous Frameworks

This paper describes two copper(I) supramolecules with the same anion and cation but quite different topologies
and properties. The reaction of [Cu(CH3CN)4]PF6 and 1,2,4,5-tetracyanobenzene (TCNB) leads to two novel
polymeric coordination compounds, [Cu2(TCNB)3](PF6)2(Me2CO)4(1) and [Cu2(TCNB)3](PF6)2 (2), depending
on the solvents used. The crystal structures have been determined by single-crystal X-ray diffraction. Crystal
data are as follows. 1:  C21H15N6O2CuPF6, monoclinic, P21/a, a = 11.553(4) Å, b = 16.135(7) Å, c = 15.046(3)
Å, β = 108.08(2)°, Z = 4. 2:  C15H3N6CuPF6, orthorhombic, Cmcm, a = 28.282(3) Å, b = 10.337(3) Å, c =
16.285(4) Å, Z = 16. In both polymers, copper(I) ions have similar pseudotetrahedral environments and the four
coordination sites are fully occupied by the four bridging ligands, two μ2-TCNB and two μ4-TCNB groups. Polymer
1, obtained in acetone, revealed a two-dimensional zigzag sheet network between copper(I) ions, whereas 2,
synthesized in methylethyl ketone, displayed a three-dimensional porous framework with different functional
groups (or atom) in different cavities. The redox, magnetic, and conductive behaviors of both complexes are
discussed. It is demonstrated that the two complexes give different physicochemical properties.