Coordination Polymers of Copper(I) Halides

Abstract

A total of 21 complexes of CuX (X = Cl, Br, I) with bridging ligand (B = 4,4'-dipyridyl (Bpy), pyrazine (Pyz), quinoxaline (Quin), phenazine (Phz), 1,4-diazabicyclo[2.2.2]octane (DABCO), and hexamethylenetetramine (HMTA)) have been synthesized. The products show two stoichiometries: [CuXB] (type 1) and [(CuX)2B] (type 2). Both types can be obtained for B = Bpy, depending on the conditions of preparation. In these cases, the type 2 stoichiometry is the kinetic product. Type 2 complexes only are found for B = Pyz (X = I), Quin, Phz, DABCO, and HMTA. Type 1 complexes form for Pyz (X = Cl, Br). Thermogravimetic analyses of the complexes reveal the general decomposition trend: 1 --> 2 --> [(CuX)2B(1/2)] --> CuX. The X-ray crystal structure of [CuBr(Pyz)] (type 1) features copper atoms bridged by Br and Pyz, forming 2D sheets of fused rectangular Cu4Br2(Pyz)2 units. The X-ray structure of [(CuI)2(Quin)] (type 2) shows 2D layers composed of [Cu2I2]infinity "stair step" chains which are cross-linked by Quin ligands. A total of 16 complexes of CuXL (L = P(OPh)3) with bridging ligand (B = those above and 1,4-dimethylpiperazine (DMP)) have also been prepared. All of these products, except those of HMTA, are of type 3 formulation, [(CuXL)2B]. The HMTA products have the formula [CuX(HMTA)], type 4. Thermal decomposition of the type 3 and 4 complexes occurs with initial loss of B, L, or both. The X-ray structures of [(CuBrL)2(Bpy)] and [(CuBrL)2(Pyz)] (type 3) reveal 1D chains formed from rhomboidal (LCu)2Br2 units linked by the B ligand. The type 4 structure of [CuBrL(HMTA)] is shown by X-ray to be a simple halide-bridged dimer.

Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I)-copper (II) Complex: {[Bis(ethylenediamine) Copper (II)] Bis[diiodocuprate (I)]}

“…Cu / en + CH 3 (Figure 1). In a second reversing anodic sweep another anodic peak (E A2 = 0.61 V) corresponding to the reoxidation of the product of cathodic peak at E C2 = 0.09 V appeared.…”

“…Suitable organic ligands favoring structure-specific self-assembly are the bases for the construction of coordination architectures. On the other hand, copper halides have been successfully used for the synthesis of uncharged coordination polymer arrays [2][3][4]. Various factors, such as the stiochiometric metal-to-ligand ratio, the halide and the nature and substitution of the ligand have been shown to influence the form of the copper-halide motifs and the structures of the resulting coordination polymer [2,3].…”

“…On the other hand, copper halides have been successfully used for the synthesis of uncharged coordination polymer arrays [2][3][4]. Various factors, such as the stiochiometric metal-to-ligand ratio, the halide and the nature and substitution of the ligand have been shown to influence the form of the copper-halide motifs and the structures of the resulting coordination polymer [2,3]. Recently, increasing attention has been paid to the use of flexible bridging units in the construction of supramolecular architectures [5,6] and this approach is attractive because the flexibility and conformation freedoms of such ligands offer the possibility for the construction of unprecedented frameworks with tailored properties and functions [7].…”

Synthesis, Crystal Structure and Thermal Reactivity of New Copper(I) Halide Pyrimidine‐Containing Coordination Polymers

“…The ligand-rich 1:2 coordination polymers with pyrazine have an identical topology of the coordination network to the present pyrimidine compounds. CuX single chains (X ϭ Cl, [39] Br [15] ) are observed as the CuX substructure, and these are connected into layers by the pyrazine ligands. If the N-donor atoms are located in the 1-and 2-positions, like in pyridazine, the topology of the coordination network in the 1:1 compounds is completely different.…”

Two-Dimensional Coordination Polymer of 3-(Methylthio)-1-thiomorpholinopropan-1-one Propagated by Rhomboid Cu-I2-Cu Linker

“…1 In view of the structural and photophysical properties, the chemistry of copper(I) coordination polymers built from amine functional group has been widely studied. 2 Our interest in coordination chemistry has been mainly on a new type of cyclic 3,4 and acyclic 5 ligands with soft donor atoms, since these are expected to exhibit novel coordination properties toward thiaphilic metal species, such as silver(I) and copper(I) salts. As an extension of our programs, we are currently working on the synthesis of a novel sulfur-containing ligand system involving 3-(methylthio)-1-thiomorpholinopropan-1-one (L) as an asymmetric building block.…”