Abstract
To investigate the influence of different 5-functionalized isophthalate ligands on the self-assembly and structures of Zn(ii)-based coordination polymers (CPs), we selected four 5-functionalized isophthalate ligands coordinated with 4,4′-bipyridyl (bpy) and Zn(ii) salt, and four new CPs, namely, {[Zn(EtOip)(bpy)]·2H2O}n (1), {[Zn(PrOip)(bpy)]·2H2O}n (2), [Zn(nBuOip)(bpy)]n (3) and [Zn(nPeOip)(bpy)]n (4) (where EtOip = 5-ethoxyisophthalate, PrOip = 5-n-propoxyisophthalate, nBuOip = 5-n-butoxyisophthalate and nPeOip = 5-n-pentyloxyisophthalate), were prepared under hydrothermal conditions. Moreover, we considered changing the features of the N-ligands (length), which are expected to alter the structural diversities and properties of the resultant CPs. We used 1,2-bis(4-pyridyl)ethene (bpe) to replace bpy; and obtained four new coordination polymers (CPs), namely, {[Zn(EtOip)(bpe)]·H2O}n (5), {[Zn(PrOip)(bpe)]·H2O}n (6), {[Zn(nBuOip)(bpe)]·0.5DMF}n (7) and [Zn(nPeOip)(bpe)]n (8). All of these compounds were characterized by single crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction measurements. Single-crystal X-ray analysis reveals that the structure of complexes 1–4 are very similar, although different functionalized-isophthalate ligands are employed. Complexes 5, 6 and 7 possess a two-dimensional (2D) layered structure, and the 2D framework of complexes 5 and 7 can be rationalized to be a threefold interpenetrating four-connected {44·62} topological sql network, while 6 exhibits a twofold interpenetrating 4-connected 2D framework. Compound 8 features a 6-connected 3D topology net based on a novel bimetallic unit [(Zn)2(CO2)2] linked by mixed nPeOip and bpe ligands. Moreover, thermal and photoluminescence properties of the synthesized complexes were also studied in detail.
Highlights
Over the past few decades, the rational design and synthesis of novel coordination polymers (CPs) has been of great interest in coordination chemistry and material science due to the intriguing architectures and topologies of the CPs, and for their potential applications as functional materials in numerous elds, such as luminescence, catalysis, gas adsorption/separation, magnetism and so forth.1–13 Despite that a comparatively large number of interesting coordination polymers with intricate structural architectures have been reported to date, the design and construction of multi-functionalCPs with desired structures and properties remains a signi cant challenge for chemists
In recent years, functionalized polycarboxylic acid derivatives have been extensively used as multifunctional organic ligands in the formation of coordination frameworks owing to their high stability, various coordination modes and strong coordination ability toward transition metal ions
Eight Zn(II) coordination polymers have been successfully synthesized under hydrothermal conditions by the
Summary
Over the past few decades, the rational design and synthesis of novel coordination polymers (CPs) has been of great interest in coordination chemistry and material science due to the intriguing architectures and topologies of the CPs, and for their potential applications as functional materials in numerous elds, such as luminescence, catalysis, gas adsorption/separation, magnetism and so forth.. CPs with desired structures and properties remains a signi cant challenge for chemists. This is because many intrinsic and external factors, such as the coordination nature of the metal centers, the structural characteristics of the organic ligands, stoichiometry, temperature, solvent, the pH of the solution and so on, may considerably in uence the formation of the resulting CPs.. In recent years, functionalized polycarboxylic acid derivatives have been extensively used as multifunctional organic ligands in the formation of coordination frameworks owing to their high stability, various coordination modes and strong coordination ability toward transition metal ions. Among them, 5-functionalized isophthalates are good candidates within coordination and supramolecular chemistry because their two V-shaped carboxylate groups may bridge metal ions or metal clusters via versatile coordination modes similar to that of isophthalate. For example, McCormick et al found that the topology of CPs is dependent on the combination of solvent
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