STRUCTURAL CONTROL OF COPPER(I) COORDINATION POLYMERS - CONSTRUCTION OF ONE-, TWO-, AND THREE-DIMENSIONAL FRAMEWORKS OF TETRAHEDRAL COPPER(I) IONS BRIDGED BY DICYANOBENZENE DERIVATIVES

摘要

With the use of three dicyanobenzene derivatives as bridging ligands, four copper(I) coordination polymers, [Cu(dchq)(2)](ClO4)(Me2CO)(2) (1; dchq = 1,2-dicyanohydroquinone), [Cu(ipn)(2)[(PF6)(Me2CO) (2; ipn = 1,3-dicyanobenzene), and [Cu(dmtpn)(2)](X)(dmtpn)(THF) (3a (X = BF4), 3b (X = ClO4); dmtpn = 2,5-dimethylterephthalonitrile) were synthesized and characterized. Single-crystal X-ray analyses revealed that all copper(I) ions in these complexes have tetrahedral geometry and are coordinated by four ligands which also coordinate to the next copper ions, resulting in the formation of coordination polymer compounds. The polymer framework of 1 consists of one-dimensional chains that run along the a-axis direction and weakly interact with each other through pi-pi interactions between the dchq molecules and through hydrogen bonding. 2 has a two-dimensional sheet with a square arrangement of copper(I) ions. Stacking of the square lattice in the c-axis direction forms cavities in which the acetone molecules and PF6- anions are incorporated. Both 3a and 3b are isostructural and have triply interpenetrated three-dimensional diamond-like frameworks with pi-pi stacking columns of alternately coordinated and uncoordinated dmtpn molecules. It is demonstrated that the dimensionality of the polymer structures can be successfully controlled by the relative positions of two CN groups in the bridging Ligands. Crystallographic data are as follows. 1: C22H20CuCIN4O10, monoclinic, C2/c, a = 19.514(2) Angstrom, b = 10.526(2) Angstrom, c = 12.276(1) Angstrom, beta = 96.839(8)degrees, Z = 4. 2: C19H14CUF6N4OP, orthorhombic, P2(1)2(1)2(1), a = 12.743(2) Angstrom, b = 15.026(3) Angstrom, c = 11.362(2) Angstrom, Z = 4. 3a: C34H32BCuF4N6), monoclinic, Cc, a = 9.599(3) Angstrom, b = 27.298(5) Angstrom, c = 13.367(3) Angstrom, beta = 105.45(2)degrees, Z = 4. 3a: C34H32ClCuN6O5, monoclinic, Cc, a = 9.590(7) Angstrom,b = 27.429(3) Angstrom, c = 13.416(4) Angstrom, beta = 105.80(3)degrees, Z = 4. [References: 34]