Cyanide Coordination Polymers Research Articles

Anisotropic Thermal Expansion of Structurally Related Lanthanide-Mercury(II) Cyanide Coordination Polymers.

Three sets of related lanthanide-mercury(II) cyanide coordination polymers were synthesized by the reaction of LnCl3·xH2O (Ln = Ce, Nd, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu) with Hg(CN)2 and structurally characterized. [Ce(OH2)5][Hg(CN)2Cl]3·2H2O is a 3-D material with sheet-based architecture; its thermal expansion behavior shows uniaxial negative thermal expansion (-18.3(8), 39(2), and 68.3(16) ppm K-1 along the a, b, and c axes, respectively). This anisotropic thermal behavior is postulated to be driven elastically by weak Hg···Cl interactions: large area expansion of the sheets causes negative thermal expansion in the perpendicular direction. Using lanthanides heavier than Ce yielded 2-D sheet-based compounds with the formula [Ln(OH2)x]2[Hg(CN)2]5Cl6·2H2O (Ln = Nd and Eu, x = 7; Ln = Gd, Tb, Dy, Ho, Tm, Yb, and Lu, x = 6). Although there was also evidence for elastic behavior within these materials, both showed uniaxial zero thermal expansion (Ln = Nd: 27.9(17), 22.4(10), and 0.6(12) ppm K-1 along the I, II, and III principal axes, respectively; Ln = Tb: 39.6(12), 1.1(17), and 36.1(7) ppm K-1 along the a, b, and c axes, respectively). Despite their similar structural architecture, this zero thermal expansion was found to occur in different directions─within the plane of the 2-D sheets for [Nd(OH2)7]2[Hg(CN)2]5Cl6·2H2O but in the direction perpendicular to the 2-D sheets for [Tb(OH2)6]2[Hg(CN)2]5Cl6·2H2O. Overall, this system of compounds reveals the delicate relationship between coordination polymer structure and thermal expansion.

Fabrication of a one‐dimensional copper(I) cyanide bearing 4,4′‐bis(imidazoly)biphenyl) polymer as a recyclable luminescent sensing material for sensitive detection of nitrofurazone

• A new 1D Cu(I)-cyanide coordination polymer (CP) bearing 4,4′-bis(imidazoly)biphenyl synthesized. • The CP forms 2D supramolecular architecture through π•••π interactions exhibited luminescent properties. • The CP used as luminescent sensor to detect antibiotics especially nitrofurazone. A new cyanide-bridged coordination polymer with formula {[C u 1 2 (CN)( bb ) 2 ]·NO 3 ·H 2 O} n ( 1 ) (bb = 4,4′-bis(imidazoly)biphenyl), has been synthesized and characterized by microanalyses, FTIR and single crystal X-ray diffraction. The single crystal X-ray studied indicated that 1 possesses a parallel one-dimensional (1D) chain, which is woven to produce a 2D supramolecular architecture held by π···π interactions between imidazolyl rings and phenyl rings with separation of 3.873 Å and 3.789 Å, respectively. The photoluminescence sensing investigation on 1 revealed that it could be used as a recyclable fluorescent sensor for antibiotics and the polymer offers sensitive and selective detection of nitrofurazone (NFZ), with high K SV value (1.01 × 10 3 M − 1 ) and low detection limit (1.53 ppm). The plausible mechanism using which the CP exhibited sensing of antibiotics has been proposed using theoretical calculations. A new Cu(I)-cyanide coordination polymer synthesized and used as sensor for antibiotics

Microporous prussian blue analogs and their application for environmental remediation: A deeper look from the structure-property-functionality perspective

The current review aims to provide the readers with an updated and explanatory overview of the PBA and related materials and how their structural features make them suitable for various environmental applications. Here we review the relevant structural aspects of the cyanide coordination polymers, mainly PBA, the most studied subfamily up to date, to describe this family of compounds better. Their porous nature, large surface area, cavities, and tunable composition stand out as attractive properties of PBA or hybrid-PBA for water and air decontamination. The most distinguished physicochemical properties and how they determine the versatility and broad scope of applications for these materials are herein discussed. A section is dedicated to the different engineering strategies of PBA, where the synergy between the components enhances the properties and performance of the new materials. The use of these compounds in adsorption, ionic exchange, desalinization, and advanced oxidation processes is described based on the tight structure-properties-functionality relationship. Some final considerations on the future potentials and limitations of cyanide coordination polymers are given from the authors' point of view. Application of microporous Prussian blue analogs in water and air decontamination through ionic exchange, adsorption, photocatalysis, sequestering, and other processes. • Physicochemical properties of cyanide-based microporous coordination polymers. • Structure-property-application relation for PB and PBA materials. • Engineering strategies for PBA with enhanced performance. • Water and air decontamination strategies using PBA materials.

2D Network overtakes 3D for photocatalytic hydrogen evolution.

3-Dimensional (3D) cyanide coordination polymers, typically known as Prussian blue Analogues (PBAs), have received great attention in catalysis due to their stability, easily tuned metal sites, and porosity. However, their high crystallinities and relatively low number of surface-active sites significantly hamper their intrinsic catalytic activities. Herein, we report the utilization of a 2-dimensional (2D) layered cobalt tetracyanonickelate, [Co-Ni], for the reduction of protons to H2. Relying on its exposed facets, layered morphology, and abundant surface-active sites, [Co-Ni] can efficiently convert water and sunlight to H2 in the presence of a ruthenium photosensitizer (Ru PS) with an optimal evolution rate of 30 029 ± 590 μmol g-1 h-1, greatly exceeding that of 3D Co-Fe PBA [Co-Fe] and Co-Co PBA [Co-Co]. Furthermore, [Co-Ni] retains its structural integrity throughout a 6 hour photocatalytic cycle, which is confirmed by XPS, PXRD, and Infrared analysis. This recent work reveals the excellent morphologic properties that promote [Co-Ni] as an attractive catalyst for the hydrogen evolution reaction (HER).

Partial Hydrolysis of Cyanide Coordination Polymers Induced by a Pillar Ligand with Optimized Electrochemical Kinetics for Rechargeable Alkaline Batteries.

Coordination polymers are promising cathode materials for rechargeable alkaline batteries. Therefore, the precise modulation of these cathodes by chemical structure and in-depth structure transform study is necessary. Here, two model coordination polymer battery cathodes were designed to demonstrate the dynamic structure-performance relationship. We studied the electrochemical performance of two kinds of nickel-based coordination polymer, comprising a planar 2D cyanide-bridged network and a 3D cyanide-bridged network pillared by pyrazine molecules. The 2D coordination polymer showed serious voltage degradation with poor rate capability, whereas the 3D coordination polymer exhibited stable voltage output coupled with high rate at various current densities. The investigation revealed the underlining relationship of plateau voltage degradation and hydrolysis process of electrodes. It was revealed that the pyrazine pillar molecules in the 3D coordination polymer could suppress the hydrolysis and lead to the in situ formation of partially hydrolyzed structure with excellent electrochemical kinetics; this exhibited obvious smaller peak separation (27 mV compared with 149 mV) and hence an almost twofold increase in capacity retention (31.9 to 50.0 %) and energy density retention (18.2 to 35.9 %) at 10 A g-1 .

A novel three-dimensional copper(I) cyanide coordination polymer constructed from various bridging ligands: synthesis, crystal structure and characterization.

The cyanide ligand can act as a strong σ-donor and an effective π-electron acceptor that exhibits versatile bridging abilities, such as terminal, μ2-C:N, μ3-C:C:N and μ4-C:C:N:N modes. These ligands play a key role in the formation of various copper(I) cyanide systems, including one-dimensional (1D) chains, two-dimensional (2D) layers and three-dimensional (3D) frameworks. According to the literature, numerous coordination polymers based on terminal, μ2-C:N and μ3-C,C,N bridging modes have been documented so far. However, systems based on the μ4-C:C:N:N bridging mode are relatively rare. In this work, a novel cyanide-bridged 3D CuI coordination framework, namely poly[(μ2-2,2'-biimidazole-κ2N3:N3')(μ4-cyanido-κ4C:C:N:N)(μ2-cyanido-κ2C:N)dicopper(I)], [Cu2(CN)2(C6H6N4)]n, (I), was synthesized hydrothermally by reaction of environmentally friendly K3[Fe(CN)6], CuCl2·2H2O and 2,2'-biimidazole (H2biim). It should be noted that cyanide ligands may act as reducing agents to reduce CuII to CuI under hydrothermal conditions. Compound (I) contains diverse types of bridging ligands, such as μ4-C:C:N:N-cyanide, μ2-C:N-cyanide and μ2-biimidazole. Interestingly, the [Cu2] dimers are bridged by rare μ4-C:C:N:N-mode cyanide ligands giving rise to the first example of a 1D dimeric {[Cu2(μ4-C:C:N:N)]n+}n infinite chain. Furthermore, adjacent dimer-based chains are linked by μ2-C:N bridging cyanide ligands, generating a neutral 2D wave-like (4,4) layer structure. Finally, the 2D layers are joined together via bidentate bridging H2biim to create a 3D cuprous cyanide network. This arrangement leads to a systematic variation in dimensionality from 1D chain→2D sheet→3D framework by different types of bridging ligands. Compound (I) was further characterized by thermal analysis, solid-state UV-Vis diffuse-reflectance and photoluminescence studies. The solid-state UV-Vis diffuse-reflectance spectra show that compound (I) is a wide-gap semiconductor with band gaps of 3.18 eV. The photoluminescence study shows a strong blue-green photoluminescence at room temperature, which may be associated with metal-to-ligand charge transfer.

Synthesis and Crystal Structures of Cadmium(II) Cyanide with Branched-Butoxyethanol

Two novel 3D cadmium(II) cyanide coordination polymers with branched-butoxyethanol compounds (iBucel = iso-butoxyethanol, tBucel = tert-butoxyethanol), [{Cd(CN)2(iBucel)2}{Cd(CN)2(H2O)(iBucel)}2{Cd(CN)2}6∙2(iBucel)]n I and [{Cd(CN)2(H2O)1.06(tBucel)0.94}{Cd(CN)2(tBucel)}2{Cd(CN)2}2∙1.06(tBucel)]n II, were synthesized and characterized by structural determination. Complex I contains two distinct Cd(II) coordination geometries: octahedral and tetrahedral. In contrast, complex II contains three distinct Cd(II) coordination geometries: octahedral, square-pyramidal, and tetrahedral. In the two complexes, branched-butoxyethanol molecules behave as both a ligand and a guest in the Cd(CN)2 cavities. The framework in I contains octahedral and tetrahedral Cd(II) in a 3:6 ratio. In I, the coordination environments of octahedral Cd(II) are cis-O-Cd-O. The framework in II contains octahedral, square-pyramidal, and tetrahedral Cd(II) in a 1:2:2 ratio. In II, the coordination environment of octahedral Cd(II) is disordered trans-O-Cd-O and the axial oxygen ligand is either a water or tBucel molecule. In II, the square-pyramidal Cd(II) geometry is formed by one tBucel ligand and four cyanide ligands. The Cd(CN)2 frameworks of the two complexes exhibit different structures.

Fe-Doped Ni3 C Nanodots in N-Doped Carbon Nanosheets for Efficient Hydrogen-Evolution and Oxygen-Evolution Electrocatalysis.

Uniform Ni3 C nanodots dispersed in ultrathin N-doped carbon nanosheets were successfully prepared by carburization of the two dimensional (2D) nickel cyanide coordination polymer precursors. The Ni3 C based nanosheets have lateral length of about 200 nm and thickness of 10 nm. When doped with Fe, the Ni3 C based nanosheets exhibited outstanding electrocatalytic properties for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). For example, 2 at % Fe (atomic percent) doped Ni3 C nanosheets depict a low overpotential (292 mV) and a small Tafel slope (41.3 mV dec-1 ) for HER in KOH solution. An outstanding OER catalytic property is also achieved with a low overpotential of 275 mV and a small Tafel slope of 62 mV dec-1 in KOH solution. Such nanodot-incorporated 2D hybrid structures can serve as an efficient bifunctional electrocatalyst for overall water splitting.

Fe‐Doped Ni3C Nanodots in N‐Doped Carbon Nanosheets for Efficient Hydrogen‐Evolution and Oxygen‐Evolution Electrocatalysis

AbstractUniform Ni3C nanodots dispersed in ultrathin N‐doped carbon nanosheets were successfully prepared by carburization of the two dimensional (2D) nickel cyanide coordination polymer precursors. The Ni3C based nanosheets have lateral length of about 200 nm and thickness of 10 nm. When doped with Fe, the Ni3C based nanosheets exhibited outstanding electrocatalytic properties for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). For example, 2 at % Fe (atomic percent) doped Ni3C nanosheets depict a low overpotential (292 mV) and a small Tafel slope (41.3 mV dec−1) for HER in KOH solution. An outstanding OER catalytic property is also achieved with a low overpotential of 275 mV and a small Tafel slope of 62 mV dec−1 in KOH solution. Such nanodot‐incorporated 2D hybrid structures can serve as an efficient bifunctional electrocatalyst for overall water splitting.

One unexpected mixed-valence Cu(I,II)-cyanide coordination polymer in situ originating from the cleavage of acetonitrile

Solvothermal reaction of CuCl2·2H2O and 2-(4-pyridyl)benzimidazole (PyHBIm) in a acetonitrile-water mixed solvent afforded a mixture of [CuI2CuII(CN)2(PyHBIm)2Cl2]n (1) and [CuII(PyH2BIm)2Cl4] (2). Complex 1 is a mixed-valence 1D ribbon Cu(I,II)-cyanide coordination polymer. One Cu(II) center linearly links two Cu(I) ions via two μ2-CN bridges. XPS spectrum and bond valence sum (BVS) analysis have confirmed the mixed-valence characteristics. Cu(II) ion adopts a centrosymmetric square-planar geometry surrounded by two cyanides and two pyridyl groups. Cu(I) ions adopt a trigonal geometry coordinated by cyanide, imidazole group and Cl− anion. The cyanide ligand is in situ generated from the cleavage of acetonitrile solvent, which indicates that acetonitrile is an environmentally friend cyanating agent. The mechanism of acetonitrile in situ cleavage under solvothermal condition is explained. Complex 2 is a centrosymmetric mononuclear Cu(II) compound. Four equivalent Cl− anions lie on the equatorial plane. The protonated PyH2BIm+ cation as a monodentate ligand coordinates to Cu(II) center via pyridyl terminal.

Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers incorporating flexible N-donor ligands

Three copper(I) cyanide coordination polymers, namely [Cu8(CN)8(btmb)2]n (1), [Cu(CN)(btmb)0.5]n (2) and [Cu2(CN)2(dpa)]n (3) (btmb=1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, dpa=di(4-pyridyl)amine), were synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectra, PXRD and thermogravimetric analyses. Single-crystal X-ray diffraction analyses reveal that complex 1 is an interesting 2D double-layered network constructing from eight distinct Cu(I) centers, eight μ2-cyanides and two tetradentate cis-btmb ligands. Complex 2 is a ladder-like coordination polymer assembled by CuCN linear chain and bidentate trans-btmb linker. Complex 3 has a 2D wave-like network constructing from CuCN zigzag chain and V-shape dpa spacer. These coordination polymers are thermally stable up to 270–300°C. They emit blue luminescence originating from ligand-centered emission.

Three-Dimensional Cadmium(II) Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ethanol

The three novel cadmium(II) cyanide coordination polymers with alkoxyethanols, [Cd(CN)2(C2H5OCH2CH2OH)]n (I), [{Cd(CN)2(C4H9OCH2CH2OH)}3{Cd(CN)2}]n (II) and [{Cd(CN)2(H2O)2}{Cd(CN)2}3·2(C6H13OCH2CH2OH)]n (III), were synthesized and charcterized by structural determination. Three complexes have three-dimensional Cd(CN)2 frameworks; I has distorted tridymite-like structure, and, II and III have zeolite-like structures. The cavities of Cd(CN)2 frameworks of the complexes are occupied by the alkoxyethanol molecules. In I and II, hydroxyl oxygen atoms of alkoxyethanol molecules coordinate to the Cd(II) ions, and the Cd(II) ions exhibit slightly distort trigonal-bipyramidal coordination geometry. In II, there is also tetrahedral Cd(II) ion which is coordinated by only the four cyanides. The hydroxyl oxygen atoms of alkoxyethanol connects etheric oxygen atoms of the neighboring alkoxyethanol by hydrogen bond in I and II. In III, hexyloxyethanol molecules do not coordinate to the Cd(II) ions, and two water molecules coordnate to the octahedral Cd(II) ions. The framework in III contains octahedral Cd(II) and tetrahedral Cd(II) in a 1:3 ratio. The Cd(CN)2 framework structures depended on the difference of alkyl chain for alkoxyethanol molecules.

Vibrational–Structural Combined Study into Luminescent Mixed Copper(I)/Copper(II) Cyanide Coordination Polymers

Herein, we report the characterization of a series of CuCN-based coordination polymers that display different crystal packing and electronic properties, namely, [Na2Cu(CN)3·3H2O]n (1), [Cu4(CN)5(NH3)2(H2O)]n (2), [Cu3(CN)4(NH3)3]n (3), [Cu3(CN)3(O)0.25(NH3)]n (4), [Cu5(CN)6(NH3)4]n (5), and [Cu5(CN)6(NH3)2]n (6). Spectroscopic evidence of the presence of ammonia molecules coordinated to the metal centers is provided, in particular for 4, which is a new structure. The characterization has been performed by single-crystal XRD (SCXRD), micro- IR spectroscopy, micro-Raman spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The photophysical properties have been studied through solid-state luminescence spectroscopy by acquiring the emission and excitation spectra and evaluating the emission quantum yields, which is an approach that has recently grown in importance in the solid-state field. The goals of this work are (1) to elucidate the correlation between the luminescence properties and the presence of either CuI or mixed CuI/CuII oxidation states, (2) to evaluate the presence of NH3, H2O, or both in the polymers through a combined crystallographic–spectroscopic study, and (3) to rationalize the supramolecular architecture and its influence on the resulting luminescence.

Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250–350 °C. Complexes 1–3 show similar orange emission band at 602 nm originating from LMCT mechanism.

In situ construction of four copper(I) cyanide coordination polymers: crystal structures, fluorescence and catalytic properties

Four Cu(I) cyanide coordination polymers, namely [Cu(L1)(CN)] n (1), [Cu2(L2)(CN)2] n (2), [Cu2(L3)(CN)2] n (3) and [Cu2(L4)(CN)2] n (4) (L1 = 4,4′-bis(1,2,4-triazolyl-1-yl)-biphenyl, L2 = 1,4-bis(5,6-dimethylbenzimidazole)butane, L3 = 1,3-bis(2-methylbenzimidazole)propane, L4 = 1,5-bis(5,6-dimethylbenzimidazole)pentane), were synthesized and structurally characterized by X-ray single-crystal diffraction. The cyanide anions in these complexes were generated in situ by cleavage of the C–C bond of acetonitrile under hydrothermal conditions. Complex 1 possesses a 1D infinite ladder-like chain structure, while complexes 2, 3 and 4 exhibit similar 2D (6,3) networks. Both 3 and 4 are further extended into 3D supramolecular frameworks by C–H···π stacking interactions. The fluorescence properties of the complexes and their catalytic activities for the degradation of Congo red azo dye in a Fenton-like process were investigated.

Three Ag(I)–cyanide coordination polymers with metal bonds tuned by N-heterocyclic ligands

Hydrothermal reactions of AgNO3, K3[Fe(CN)6] with N-heterocyclic ligands afforded three novel Ag(I)–cyanide coordination polymers, [Ag2(CN)2(tpt)]n (1), {[Ag(CN)(bpe)0.5][Ag(CN)]}n (2) and [Ag(CN)(btmb)0.5]n (3) (tpt=2,4,6-tris(4-pyridyl)-1,3,5-triazine, bpe=1,2-bis(4-pyridyl)ethane, btmb=1,2-bis(1,2,4-triazol-1-ylmethyl)benzene). In complex 1, two Ag(CN) linear chains are bridged by bidentate tpt ligand to form a ladder-like structure, which are further connected by AgAg metal bond to generate a 2D polymeric network. Complex 2 is an interesting 3D supramolecular architecture assembled by 2D [Ag1(CN)(bpe)0.5]n network and linear [Ag2(CN)]n chain combined by strong AgAg metal bond. Complex 3 is a 1D ladder-like double-chain polymer constructed from Ag–cyanide linear chains and btmb spacer, which is further extended to a 2D supramolecular network by Ag–Ag weak interaction. The Ag–Ag metal interactions play important roles in the construction of three coordination polymers. Complexes 1 and 2 are respectively thermally stable at 300 and 180°C. Complexes 1 and 3 emit strong blue luminescence.

Synthesis, Crystal Structure, Spectroscopic and Electrochemical Properties of a Copper Coordination Polymer with Unprecedented Topology

AbstractA copper cyanide coordination polymer [Cu8(CN)8(bbtz)2]n (1) [bbtz = 1,4‐bis(1,2,4‐trizal‐1‐ylmethyl)benzene] was synthesized following a synchronous redox and self‐assembly reaction under the solvothermal condition, and characterized by elemental analysis, infrared spectroscopy, and single‐crystal X‐ray diffraction. Interestingly, complex 1 exhibits a two‐dimensional conjugated pillared double‐layer architecture and an unprecedented (3,3,4)‐connected network with the point symbol (6.7.10)2(6.72)2(62.73.10) topology. Moreover, the thermogravimetric analysis indicates complex 1 has highly thermal stability, and the solid‐state emission spectrum for its crystalline material displays a strong green luminescence band (λmax = 565 nm) at room temperature. The electrochemical behavior of complex 1 is determined by the scan rates in the range from –0.5 to +0.3 V at room temperature, and exhibits different redox processes.

Two-level hierarchical entangled framework in a novel copper(I) coordination polymer with multiform helical features and unprecedented self-penetrated subnet

One new copper(I) cyanide coordination polymer [Cu4(CN)4(tib)]n (1) (tib=1,3,5-tris(1-imidazolyl)benzene) has been solvothermally synthesized through a synchronous redox and self-assembly reaction of copper(II) utilized as starting material, and characterized by elemental analysis, FT-IR, PXRD and single-crystal X-ray diffraction. The result shows complex 1 possesses a novel two-level hierarchical entangled 3D framework coordination polymer with multiform helical features and an unprecedented self-penetrated subnet, which belongs to the Class IIa interpenetration. The 3D subnet of complex 1 can be classified as a (102.12)(103)3 topology. Moreover, the thermal and luminescent properties and the nature of coordinate bonds of complex 1 have also been investigated.

Synthesis of a rare 3D copper cyanide compound based on 3-(5-(pyridin-4-yl)-1H-1,2,4-triazol-3-yl)pyridine via the transformation of acetonitrile to inorganic cyanide

One-pot solvothermal treatments of acetonitrile, water, LiOH, Cu(CH3COO)2·H2O and 3-(5-(pyridin-4-yl)-1H-1,2,4-triazol-3-yl)pyridine (HL) yielded a rare copper cyanide coordination polymer, [Cu2(L) (CN)]n (1). The existence of a cyanide group in compound 1 may be due to the decomposition of acetonitrile at the relatively high temperature (160°C) and autogenous pressure of the reaction. Compound 1 has been characterized by single-crystal X-ray diffraction, XRPD, IR, and elemental analysis. Compound 1 is a 3D copper cyanide coordination polymer, and a ({6.8.10}2{6.8^3.10^2}) topology in 1 is created. In addition, the optical and catalytic properties have been investigated.

Oxidative coupling of 2-aminophenol to 2-amino-phenoxazine-3-one catalyzed by organotin (IV)–copper (I) cyanide coordination polymers as heterogeneous catalysts

The activity of organotin (IV)–copper (I) cyanide coordination polymers [Ph3SnCu (CN)2·L] where L=1,2-bis(4-pyridyl)ethane (bpe) 1, 4,4′-bipyridine (bpy) 2, methylpyrazine (mepyz) 3 or trans-1,2-bis(4-pyridyl)ethene (tbpe) 4 has been investigated as heterogeneous catalysts for the biomimetic oxidative coupling of 2-aminophenol (OAP) to 2-aminophenoxazine-3-one (APX). The rate of OAP consumption was determined by measuring the amount of dioxygen consumed using a gas burette. All the coordination polymeric catalysts showed high activity for auto-oxidation of OAP. The coordination polymer 4 has been found to be the most reactive catalyst. The rate of auto-oxidation reaction of OAP catalyzed by the coordination polymer 4 has been found to increase with increasing the pH from 7 to 9 then decreased at higher pH. The rate of auto-oxidation reaction showed linear dependence on catalyst concentration and pressure of dioxygen. The rate of reaction has been found to fit a Michaelis–Menten kinetic model for saturation of catalyst sites with increasing OAP concentration. The catalyst 4 showed no deactivation after six runs.