Structural Control of Copper(I) Coordination Polymers:  Construction of One-, Two-, and Three-Dimensional Frameworks of Tetrahedral Copper(I) Ions Bridged by Dicyanobenzene Derivatives

Abstract

With the use of three dicyanobenzene derivatives as bridging ligands, four copper(I) coordination polymers, [Cu(dchq) 2 ](ClO 4 )(Me 2 CO) 2 (1; dchq ) 1,2-dicyanohydroquinone), [Cu(ipn) 2 ](PF 6 )(Me 2 CO) (2; ipn ) 1,3dicyanobenzene), and [Cu(dmtpn) 2 ](X)(dmtpn)(THF) (3a (X ) BF 4 ), 3b (X ) ClO 4 ); dmtpn ) 2,5dimethylterephthalonitrile) 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 π-π interactions between the dchq molecules and through hydrogen bonding. 2 has a twodimensional 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 PF 6 -anions are incorporated. Both 3a and 3b are isostructural and have triply interpenetrated three-dimensional diamond-like frameworks with π-π 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: C 22 H 20 CuClN 4 O 10 , monoclinic, C2/c, a ) 19.514(2) Å, b ) 10.526(2) Å, c ) 12.276(1) Å, β ) 96.839(8)°, Z ) 4. 2: C 19 H 14 CuF 6 N 4 OP, orthorhombic, P2 1 2 1 2 1 , a ) 12.743-(2) Å, b ) 15.026(3) Å, c ) 11.362(2) Å, Z ) 4. 3a: C 34 H 32 BCuF 4 N 6 O, monoclinic, Cc, a ) 9.599(3) Å, b ) 27.298(5) Å, c ) 13.367(3) Å, β ) 105.45(2)°, Z ) 4. 3b: C 34 H 32 ClCuN 6 O 5 , monoclinic, Cc, a ) 9.590(7) Å, b ) 27.429(3) Å, c ) 13.416(4) Å, β ) 105.80(3)°, Z ) 4.

Copper and cadmium coordination polymers of di-3-pyridinylmethanone: Subtle anion effect on the dimensionality of Cd(II) frameworks

“…In the design of coordination polymers with diverse dimensionalities [1][2][3][4][5], the counter anion has been shown to play a dominant role [6][7][8][9][10][11][12]. Under normal circumstances, coordination compounds constructed from metal tetrafluoroborates and perchlorates are similar in structure because these two tetrahedral monoanions have only minor differences in their coordinating capability [13,14].…”

Syntheses and characterization of novel ruthenium complexes based on 1,3-dicyanobenzene

“…In both compounds a bimetallic complex cation is formed, with 1,3-dicyanobenzene acting as a bidentate ligand. Only a few structures involving such non linear, strongly angulated bridging ligands are reported in the literature [48,49]. Each ruthenium atom in 1cis adopts a distorted octahedral geometry, with the nitrogen atom cis to the chlorine atom.…”

[B(O–C6H4–CN)4]– based Silver and Copper Coordination Polymers

“…E(p-C 6 H 4 -CN) 4 (E = C, Si) [12] or polycyanobenzenes. [13] Additionally, many boron containing anions are used in coordination polymer synthesis. Metal salts containing the [B(CN) 4 ] -anion can be regarded as coordination polymers due to the presence of CN-metal contacts.…”