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

Abstract

This paper describes two copper(I) supramolecules with the same anion and cation but quite different topologies and properties. The reaction of [Cu(CH(3)CN)(4)]PF(6) and 1,2,4,5-tetracyanobenzene (TCNB) leads to two novel polymeric coordination compounds, [Cu(2)(TCNB)(3)](PF(6))(2)(Me(2)CO)(4)( )()(1) and [Cu(2)(TCNB)(3)](PF(6))(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: C(21)H(15)N(6)O(2)CuPF(6), monoclinic, P2(1)/a, a = 11.553(4) Å, b = 16.135(7) Å, c = 15.046(3) Å, beta = 108.08(2) degrees, Z = 4. 2: C(15)H(3)N(6)CuPF(6), 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 &mgr;(2)-TCNB and two &mgr;(4)-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.

Hydrothermal synthesis, structural investigation, and magnetic properties of 2-D layered lanthanide (Ln = Pr, Eu, Gd, Tb, and Er) coordination polymers possessing infinite 1-D nanosized cavities

“…Coordination modes of multidentate oxygen donor ligands and flexible coordination geometry as well as variable coordination numbers of lanthanides are responsible to generate various LOFs [6-10]. It is, however, difficult to predict the resultant LOF structure as there are parameters involved such as coordination geometry of ligand, solvent polarity, pH of solution [11][12][13][14][15], metal to ligand ratio [11][12][13][14][16][17][18], reaction time, and temperature [11][12][13][14][16][17][18]. Among these factors, pH plays a major role for construction of coordination polymers.…”

Cu2+‐Mediated Dehydrogenative Coupling and Hydroxylation of an N‐Heterocyclic Ligand: From Generation of a New Tetratopic Ligand to the Designed Assembly of Three‐Dimensional Copper(I) Coordination Polymers

“…The three interpenetrating networks are shown in Figure 1 c. We are aware of only three examples of coordination polymers with this topology: the structures of Cd(CN) 2 (H 2 O) 2/3 ⋅ t BuOH and [Cu 3 (pytac) 6 ]⋅14 H 2 O (pytac=2‐(4‐pyridyl)thiazole‐4‐carboxylate) contain a single moganite network,11a,b while the structure of [Cu 2 (TCNB) 3 ](PF 6 ) 2 (TCNB=1,2,4,5‐tetracyanobenzene) contains two interpenetrating moganite nets 11c. This structure is particularly relevant as, like the structure of 1 , it contains tetrahedral Cu I atoms bridged by potential tetradentate ligands, only one‐third of which are actually tetradentate and act as square‐planar nodes, while the other two‐thirds are simply bidentate.…”

Frameworks by Solvent‐Free Synthesis of Rare Earth Chlorides with Molten 1,3‐Benzodinitrile and Tailoring of the Particle Size: ∞3[LnCl3{1,3‐C6H4(CN)2}], Ln = Y, Dy, Ho, Er, Yb

“…[3][4][5][6][7][8] This chemistry therefore strongly depends on the solvents used. [24][25][26][27][28][29][30] This also proves a formidable synthesis strategy for nitrile-containing coordination polymers [31][32][33] including 1,4-benzodinitrile frameworks [34] that were obtained from reactions of anhydrous Ln chlorides with melts of 1,4-benzodinitrile. in the melt of a ligand, can also be utilized.…”