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

Abstract

Reaction of copper(I) chloride with pyrimidine in acetonitrile leads to the formation of the ligand‐rich 1:1 compound poly[CuCl(μ2‐pyrimidine‐N,N′)] (1). “Zig‐zag”‐like CuCl chains are found in the crystal structure that are connected by the pyrimidine ligands to form layers. This compound loses half of its ligands upon heating and transforms into the new l2:1 coordination polymer poly[(CuCl)2(μ2‐pyrimidine‐N,N′)] (2). In this structure, ladder‐like CuCl double chains occur which are connected by the pyrimidine ligands to form layers. If copper(I) iodide is used in the synthesis, the new 1:1 coordination polymer poly[CuI(μ2‐pyrimidine‐N,N′)] (3) forms. In contrast to compound 1, CuI single chains and (CuI)2 dimers are found as the CuX substructure, and these are connected by the ligands to form sheets. On heating this compound a similar behaviour as for compound 1 is observed, and a transformation into the new 2:1 compound poly[(CuI)2(μ2‐pyrimidine‐N,N′)] (4) occurs. This compound is not isotypic to 2 even though the topology of the coordination network is identical (CuI double chains are connected into layers by the pyrimidine ligands). The thermal behaviour of the known compounds poly[CuBr(μ2‐pyrimidine‐N,N′)] (5) and poly[(CuBr)2(μ2‐pyrimidine‐N,N′)] (6) was also investigated. A transformation of the ligand‐rich 1:1 compound 5 into the 2:1 compound 6 is also observed in the thermal decomposition reaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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

“…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].…”

Construction of [Cu n I n ]-based coordination polymers via flexible benzimidazolyl-based ligands

“…These motifs could be further connected by N-heterocyclic linkers to form more complex [Cu n I n ]-based frameworks. Preparation of such compounds has been reported to be affected by many factors such as CuI-to-ligand ratio, flexibility and rigidity of the ligands, solvents and temperatures [29,36].…”

[Cu2Br2(BPP)]n (BPP=1,3-bis(4-pyridyl)propane): A luminescent 2-D inorganic–organic hybrid coordination network with 1-D copper (I) chains bridged by trans-Br atoms

“…They are: (a) square (rhomboid) dimer; (b) cubane tetramer; (c) diamondoid tetramer; (d) zigzag chain; (e) double-stranded ladder and (f) hexagonal grid chain, respectively. Besides their intriguing topology [1][2][3][4][5], copper (I) halide complexes have attracted wide interest for their rich photophysical properties [7][8][9][10]. The presence of direct CuÁ Á ÁCu interactions has been proved to be one of the crucial causes to the luminescent properties in such species [7].…”

“…Several of them in various dimensionality including 1-D chain-like, 2-D layered and 3-D extended structures have been synthesized and characterized [1][2][3][4][5][6]. As a summary of the reported structures, the basic structural skeletons of copper (I) halides (CuX) are listed in Scheme 1.…”