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International audience; A zinc(II) complex of polypyazole containing ligand namely, [Tp*ZnCl] (Zn1) {Tp* = tris(3,5-dimethylpyrazolyl)borate}, along with its zinc(II) bound hydroxo complex [Tp*Zn–OH] (Zn2) were synthesized and characterized by FT-IR, Raman, 1H NMR techniques and elemental analysis. In alkaline solution (0.1 M KOH), the Zn2 modified glassy carbon (GC), namely GC–Zn2, was investigated as a molecular electrocatalyst for the hydrogen evolution reaction (HER). Different quantities (ca. 0.1–0.5 mg cm–2) of Zn2 were loaded on GC electrodes to make various GC–Zn2 electrodes. These electrodes were utilized as cathodes in 0.1 M KOH to produce H2 using linear sweep voltammetry (LSV) measurements. The HER electrocatalytic activity of the GC–Zn2 catalyst was found to be quite high and it increased with the catalyst loading density. The top performing electrocatalyst, GC–Zn2 (0.5 mg cm–2), demonstrated considerable HER catalytic performance with a low HER onset potential (EHER) of –33 mV vs. RHE and a high exchange current density of 0.59 mA cm–2. Moreover, the top performing electrocatalyst had a Tafel slope of –152 mV dec–1 and consumed an overpotential of 135 mV to generate a current density of 10 mA cm–2. Under the same operating conditions, these HER electrochemical kinetic parameters were found to be not remarkably far from those determined for commercial Pt/C (–10 mV vs. RHE, 0.88 mA cm–2, 108 mV dec–1 and 110 mV to yield a current density of 10 mA cm–2). In addition, the most active molecular electro-catalysts for H2 production from aqueous alkaline electrolytes were found to be comparable to the HER electrochemical kinetic parameters reported here for the GC–Zn2 electrocatalyst. Using 5000 cycles of repetitive cyclic voltammetry and 48 h of chronoamperometry measurements, the best electrocatalyst’s stability and long term durability were tested. It exhibited high stability for the HER catalytic activity.

The reaction of potassium tetracyanocupprate(I) with triethyltin bromide in presence of phenanthroline (Phen) and quinoxaline (Qox) in acetonitrile via ultrasonic radiation yielded two new nano-supramolecular coordination polymers (SCP) of the type: [Cu2(CN)4(Et3Sn)2(Phen)2] SCP1 and [Cu2(CN)3(Et3Sn)(Qox)] SCP2. The obtained polymers were characterized using elemental and thermal analyses, as well as FT-IR, UV–vis, fluorescence, 1H NMR, and MS spectroscopes. Spectral and analytical features led to the conclusion that both Phen and Qox behave as bidentate ligands and the proposed formulae of SCP1 and SCP2 have the bimetallic nature, in which the geometry around Cu(I) atoms in SCP1 is tetrahedral and planar trigonal. While in SCP2, the Cu(I) has a trigonal plane geometry. Thermal analysis studies indicated that both SCP1 and SCP2 are thermally stable up to 140 °C. Additional confirmation for the structures of SCP1 and SCP2 was obtained from density functional theory (DFT) and molecular mechanics (MM+) calculations. Transmission electron microscopy (TEM) images of SCP1 and SCP2 show regular spherical-like nano-sized particles in the range of 31.24–62.13 nm and 5.16–23.90 nm, respectively. The inhibitory anti-oxidant activities of both SCP1 and SCP2 were investigated using erythrocyte hemolysis and ABTS methods and their cytotoxicity activities towards different tumor cells were also studied by MTT assay. The results showed that both the two polymers have high inhibitory anti-oxidant activities and SCP2 exhibits a significant decrease in surviving fraction of these cancer cell lines compared to SCP1.

The new host-guest ∞3[Cu2(CN)3HB] supramolecular coordination polymer (SCP1) where HB = imidazole cation, was synthesized and structurally elucidated by X-ray single crystal and elemental analyses as well as spectral investigations. The topology of SCP1 constructs of three-dimensional anionic {[Cu2(CN)3]-}∞ framework based on the mini-cycle [Cu2(μ3-CN)2] motifs with encapsulation of cationic imidazole ring. Nanoscale form (SCP1\) was obtained by ultrasonic irradiation and TEM image shows regular nanostructure with the particle size in the range of 19.25–24.35 nm. Luminescence behavior of SCP1 was investigated to detect its ability as sensor for selective determination of nitrobenzene and metal ions. SCP1 and 1\ were found to have high catalytic and photocatalytic activities for degradation of Indigo Carmine (IC) in presence of H2O2. Each catalyst was recycled without loss of catalytic efficiency. The effect of ultrasonic and UV-irradiation and the degradation mechanism were also investigated.

A new mixed ligand complex, viz., [Ni(Tren)(Barb)(H2O)](Barb)(Barb-H)•2H2O (NiC) {Tren = tris(2-aminoethyl)amine and Barb = 5,5-diethlybarbiturate} has been synthesized and characterized. The nickel(II) complex was grafted to g-C3N4, forming NiC@g-C3N4. The obtained NiC complex and its hybrid material NiC@g-C3N4 were characterized by means of FT-IR, TGA-DSC, UV-vis., SEM-EDX, and XRD. Single crystal X-ray crystallography suggests that NiC exhibits NiN5O octahedral geometry. The results also show that the complex molecules are connected via N–H××××O hydrogen bonds. The complex NiC and its NiC@g-C3N4 composite showed cytotoxic effects on in vivo experiments. They also showed an increase in tissue damage markers that are represented by the increase in tissue levels of malondialdehyde (MDA) in brain, liver, kidney and heart. In parallel, both materials showed inhibitory activity for examined antioxidants such as glutathione-S-transferase (GST), superozide dismutase (SOD), glutathione (GSH), glutathione reductase (GSH-R). The destructive effects were clearer for the NiC@g-C3N4 composite compared to in liver, brain and kidney, respectively. The grafting of NiC complex in g-C3N4 is responsible for improving the catalytic activity, which is due to the synergistic effect of both components and facile recovery, as well recycling of the catalyst.

A new 3D-host-guest supramolecular coordination polymer (SCP); ∞3[(Cu3(CN)3)2.(DAHP)], 1 [1,7-diaminoheptane=.(DAHP)] had been synthesized by self-assembly at ambient conditions. X-ray single crystal diffraction of SCP 1 indicated the formation of two-fold [Cu3(CN)3]2 units containing tetrahedral copper(I) atoms which are arranged in unique way to create 3D-network. The neutral [Cu3(CN)3]2 building blocks create unique complex structure containing the minicycle [Cu2(μ3-CN)2] motif with wide cavities enable to capsulate the long chain DAHP as guest molecule. The topology of 1 had been studied by elemental analysis, IR-spectra and thermogravimetric analyses. The topology of 1 had been compared with the prototype SCP containing different aliphatic diamines which indicated the effect of structural variability and flexibility of aliphatic diamines on the network structure of these SCP. The catalytic and photo-catalytic activity of 1 was studied for mineralization of methylene blue (MB) utilizing H2O2 as an oxidant.

New single crystals and the nanoscale particles of 3D-host-guest supramolecular coordination polymers (SCP1 and 2); ∞3[(Cu3(CN)3)2.(DAHP)], [1,7-diaminoheptane=.(DAHP)] had been synthesized by self-assembly and utilizing ultrasonic radiation, respectively. X-ray single crystal diffraction of SCP1 supported the formation of the [Cu3(CN)3]2 units exhibiting tetrahedral geometry of copper(I) atoms which had been assembled in unique way to construct 3D-network. The neutral [Cu3(CN)3]2 building blocks create pretty-complex structure containing the unique [Cu2(μ3-CN)2] motif with wide cavities enable to capsulate the long chain DAHP as guest molecule. The topology and purity of 1 and 2 had been studied by elemental analysis, PXRD, IR-spectra, TEM and thermogravimetric analysis. The topology of 1 had been compared with the prototype SCPs containing different aliphatic diamines which indicated the effect of structural variability and flexibility of aliphatic diamines on the network structure of these SCP. The catalytic and photo-catalytic activity of the nanosized 2 was studied for mineralization of methylene blue (MB) utilizing H2O2 as an oxidant.

Yellow prismatic nanoparticles of the supramolecular coordination polymer (SCP) [Cu6(CN)7(C6H12N4)2(OH3)], 1 were obtained by the reaction of K3[Cu(CN)4] and hexamethylenetetramine (hmt) in presence of Me3SnCl at ambient conditions. The X-ray structure of 1 consists of many rhombic [(Cu)2µ3–(CN)2] motifs which construct eight fused cyclic rings accommodating two hmt ligands. The copper atoms exhibit pseudo-tetrahedral configuration. The cyanide ligands create the bifurcated µ3-CN bridges. The [(Cu)2µ3–(CN)2] motifs causes expansion of the structure of 1 to three dimensions while extensive H-bonds play an essential role in packing structure. SCP 1 was used as an efficient heterogeneous catalyst for oxidative mineralization of acid blue-92 (AB-92), textile dye, with H2O2. The study aimed to investigate the efficiency of recycled the catalyst 1 and the mechanism of degradation of AB-92. The morphological feature of the SCP 1 as a catalyst before and after catalysis was examined by high resolution transmission electron microscope (TEM).

1,6-Diaminohexane (DAHX) was used as template for construction of new host–guest coordination network; ∞ 3[(Cu3(CN)3)2·(DAHX)], 1. This supramolecular coordination polymer (SCP) consists of 3D-(Cu3(CN)3)2 network based on distorted tetrahedral copper(I) atoms. The extended structure of SCP 1 contains a new two-fold Cu3(µ3-CN)4 units which are assembled in unique way to adopt wide voids capable to accommodate the long chain diamine molecules. The structure of 1 was investigated by elemental analysis, IR and 1H-NMR spectroscopy, thermogravimetric analyses and X-ray single crystal diffraction. The SCP 1 acts as effective catalyst for degradation of methylene blue (MB) dye using H2O2 as oxidant. Photoluminescence probing technology was used as a sensitive probe for detecting ·OH radicals and a reaction mechanism has been suggested utilizing the redox properties of H2O2.

The reaction of K3[Cu(CN)4] and 1,4-diaminobutane (DAB) or 1,5-diaminopentane (DAP) in the presence of Me3SnCl affords two monometallic host–guest Cu(I) cyanide polymers: {[H2DAB][Cu4(CN)6]·2H2O}, 1, and{[H2DAP][H3O][Cu4(CN)7]·2H2O}, 2, with exclusion of Me3Sn+ cation. The products were characterized by physicochemical and spectroscopic methods. The structure of 1 consists of two-dimensional hexagonal sheets of (CuCN) n which stack along the b-axis creating honeycomb-shaped channels capable of encapsulating the protonated DAB and water molecules. The structure of 2 consists of a three-dimensional network of [Cu4(CN)7] with large cavities that include H2DAP and water molecules. The rhombic minicycle [Cu2(μ-CN)2] fragments represent the basic building blocks of the network structure of 2. The structures of these compounds are stabilized by hydrogen bonding. The SCP 1 and SCP 2 exhibit good catalytic and photocatalytic activities for the degradation of methylene blue (MB) in the presence of H2O2. The efficiency of recycled SCP 1 and SCP 2 and the mechanism of degradation of MB dye were also investigated.

The supramolecular coordination polymer (SCP) [Cu(CN)2(Me3Pb)phen]; 1 is formed by self-assembly of K3[Cu(CN)4], Me3PbCl and 1,10-phenanthroline (phen) ligand at ambient conditions. The copper center is coordinated to two ordered cyanide ligands and two nitrogen atoms of the phen ligand forming distorted tetrahedral configuration. The structure of 1 consists of repeating units of the tetrahedral Cu(phen)(CN)2 fragments connected by the (Me3Pb)+ cations forming1-D helical chains. The 1-D helical chains are arranged in a unique way to construct a right-helical and a left-helical chain creating a double-helical 3-D network arranged in a unique A···A···A fashion. H-bonds and π–π stacking play an important role in stabilizing the structure of 1. IR, 1H-NMR, electronic and luminescence spectra as well as thermal analysis are also investigated. The SCP 1 has high antimicrobial activity against E. coli and S. aureus and it also exhibits good activity against the fungal strains, C. albicans and A. Niger. The results of growth inhibiting effect indicated that the inhibitory effect is increased with an increase in concentration of the SCP 1.

A supramolecular coordination polymer (SCP), 3∞[Cu2(CN)4(Me3Pb)2(bpy)], 1, based on the Cun(CN)m building blocks and (Me3Pb)+ cation was synthesized in the presence of an auxiliary rigid-planar bipodal 4,4′-bipyridine (4,4′-bpy) ligand under ambient conditions. The single crystal X-ray diffraction analysis revealed that the Cu(I) sites acquire T-4 geometry and the lead atom, Pb1 assumes TBPY-5 configuration. The rhombic [Cu2(µ3-CN)2] motifs display the essential role as the main building blocks which are interconnected by the (Me3Pb)+ cations to form infinite quasi-planer sheets containing the 24-atomic C8N8Cu4Pb4 rings. These sheets are connected by the bpy ligands producing 3D-network. The wide vacant space present in the framework of 1 is occupied by a second and identical 3D-framework in that each bpy pillar of one framework passes the center of the 24-atomic ring of the complementary framework producing an inextricably interpenetrated structure. The IR, electronic absorption and emission spectra are also investigated. The SCP 1 is an effective catalyst for methylene blue degradation in presence of H2O2.

The reactions of K3[Cu(CN)4} with aliphatic diamines [urea, ethylenediamine (en) and propane-1,3-diamine (tn)] in presence of Me3SnCl or Ph3SnCl form coordination polymers (CP) with various compositions and architectures. Five coordination polymers; Ph3SnOH, 1, $$^{3}_{\infty } \left\{ {\left[ {{\text{Cu}}^{\text{II}} \left( {\text{en}} \right)_{2} {\text{H}}_{2} {\text{O}}} \right]\left[ {{\text{Cu}}^{\text{I}}_{2} \left( {\text{CN}} \right)_{4} } \right]} \right\}$$ , 2, $$^{ 3}_{\infty } \left\{ {\left[ {{\text{H}}_{ 2} {\text{tn}}} \right]\left[ {\left( {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 3} } \right)_{ 2} } \right] \cdot {\text{H}}_{ 2} {\text{O}}} \right\}$$ , 3, $$^{ 3}_{\infty } \left\{ {\left[ {{\text{Cu}}^{\text{II}} \left( {\text{tn}} \right)_{ 2} } \right]\left[ {{\text{Cu}}_{ 2}^{\text{I}} \left( {\text{CN}} \right)_{ 3} } \right]_{ 2} } \right\}$$ , 4 and K[Cu 2 I (CN)3]·(H2O), 5, have been characterized by elemental analyses, IR, mass and 1H-NMR spectroscopy, thermogravimetric analyses and X-ray single crystal diffraction. The structures of CP 2–5 are organotin free and depend on the type of the solvent and the structural variability and flexibility of the R3Sn cation and aliphatic diamine ligand. The structures contain different building blocks; [Cu2(CN)4], [Cu2(CN)3] and [Cu2(CN)3]2.

A coordination polymer (SCP), [Cu2(CN)4·(Me3Sn)2·(phen)2], 1, was constructed based on phenanthroline monohydrated (phen), trimethyltin chloride, and K3[Cu(CN)4]. The SCP 1 consists of repeating units of tetrahedral Cu(N2C2) fragments connected by (Me3Sn)+ cations which create 1-D helical chains with the phen ligands arranged on both sides of the chain. The 1-D helical chains are arranged in a unique way to form two right-helical and two left-helical chains creating a rare quartet-helical 3-D network. The quartet-helical chains are arranged in a unique A⋯A⋯A fashion forming a 3-D network structure via H-bonds and π–π stacking. Mass, electronic and luminescence spectra are also investigated. The MTT assay was used to determine the in vitro antitumor effects of SCP 1 on human breast cancer cell line, MCF-7. Cell cycle analysis revealed that SCP 1 induced apoptosis in MCF-7 breast cancer cell line. Thus, the SCP 1 selectivity exhibits specific in vitro antitumor effects against human breast cancer cell line,...

The new synthesized supramolecular complexes (SC); [Cu2(CN)4(Et3Sn)2(tbpe)], 1 and [Cu2(CN)3(Et3Sn)(bpe)], 2 (tbpe = trans-1,2-bis(4-pyridyl)ethene and bpe = 1,2-bis(4-pyridyl)ethane), were characterized by elemental analyses, electrical conductance, spectroscopic studies and thermal analyses. UV–Vis spectra and magnetic moment data suggested the tetrahedral geometry around Cu(I) atoms. The structures of the SC 1 and 2 were also theoretically studied using molecular mechanics (MM+). The structures were minimized with a semi-empirical (PM3) method. The organotin compounds represent significant advances in the clinical management of some cancer cell lines. 1 and 2 were tested as inhibitors and their citotoxicities showed potent growth inhibitory activity for hepatocellular carcinoma HePG-2, mammary gland breast cancer MCF-7, human prostate cancer PC3 and Colorectal carcinoma HCT-116 cell lines. The tested compounds showed high inhibitory anti-oxidant activity either using erythrocyte hemolysis or ABTS method.

Complexes of cobalt(II), nickel(II), copper(II), zinc(II) and Hafnium(II) of general composition [M(L)2(Cl)2] have been synthesized [L = 4-(phenylphosphinylideneamino-N-thiazolylbenzenesulfonamide]. The elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, IR, UV, NMR, SEM, EDX, thermal and EPR spectral studies of the compounds led to the conclusion that the ligand acts as a bidentate manner. The molar conductance of the complexes in fresh solution of DMSO lies in the range of 7.46–9.13 Ω-1 cm2mol‒1 indicating their non-electrolytic behavior. On the basis of analytical and spectroscopic techniques, octahedral geometry of the complexes was proposed. The ligand acts as bidentate ligand, coordinated through sulfonamide oxygen and thiazole nitrogen atoms. The ligand field parameters were calculated for Co(II), Ni(II) and Cu(II) complexes and their values were found in the range reported for a octahedral structure. The catalytic activities of the divalent metal complexes have been studied in the oxidation of cyclohexane, using environmental friendly oxidant, hydrogen peroxide. Complex with rough surface has shown higher catalytic activity compared to the other complexes. The molecular parameters of the ligand and its Co(II) and Hf(II) complexes have been calculated.

The metal–organic framework $$ ^{3}_{\infty } \left[ {{\text{Cu}}_{3} \left( {\text{CN}} \right)_{3} \cdot \left( {\text{pyz}} \right)_{ 2} } \right] $$ , 1, (pyz pyrazine) was prepared in water/acetonitrile solvent at ambient temperature from the adducts K3[Cu(CN)4], pyrazine and Me2SnCl2. The structure of 1 consists of four-coordinate Cu(1) sites exhibiting a distorted tetrahedral geometry and the linear two-coordinate Cu(2) sites. Notably distorted cages, [Cu8(CN)4(pyz)4], [Cu8(CN)6(pyz)2] and [Cu6(CN)2(pyz)4], can be considered as the basic building blocks of the structure of 1. Box-like structures create inextricably interpenetrated equivalent 3D-frameworks. The structure and spectroscopic properties of 1 were also investigated by thermal analysis and IR, mass, UV/Vis and fluorescence spectra.

Salicylidene (4-aminotoluene-3-sulfonic acid) Schiff base ligand H 2 L, and its binary and ternary Co(II), Ni(II), Cu(II) and Zn(II) complexes using 8-hydroxyquinoline (8-HOqu) and 2-aminopyridine (2-Ampy) as secondary ligands have been synthesised and characterized via elemental analysis, spectral data (IR, 1 H NMR, mass and solid reflectance), molar conductance, magnetic moment, TG–DSC measurements and XRPD analysis. Correlation of all spectroscopic data suggest that H 2 L ligand acts as monoanionic terdentate ligand with ONO sites coordinating to the metal ions via deprotonated phenolic-O, azomethine-N and sulfonate-O while 2-Ampy behaves as a neutral monodentate ligand via amino group-N and 8-HOqu behaves as a monoanionic bidentate ligand through the ring-N and deprotonated phenolic-O. The thermal behavior of these complexes shows that the coordinated water molecules were eliminated from the complexes at relatively higher temperatures than the hydrated water and there are two routes in removal of coordinated water molecules. All complexes have mononuclear structure and the tetrahedral, square planar or an octahedral geometry have been proposed. The ligand and its complexes have been screened for their antimicrobial activity against Staphylococcus aureus , Bacillus subtilis , Escherichia coli, Salmonella typhimurium , Candida albicans and Aspergillus fumigatus . Among the synthesised compounds, the binary and ternary Ni(II) complexes, ( 2 , 8 and 10 ) and ternary Zn(II) complex, ( 12 ) were found to be very effective against Candida albicans and Bacillus subtilis than all other complexes with MICs of 2 and 8 μg/mL, respectively.

The new bimetallic supramolecular coordination polymers (SCP); 3 ∞[Cu(CN)2·Me3Sn·qaz], 1 and 3 ∞[Cu2(CN)4·(Ph3Sn)2·qaz], 2 (qaz = quinazoline), are prepared in water/acetonitrile solvent at room temperature. The structure of 1 consists of the anionic Cu(CN)2 building blocks connected by the Me3Sn cations to form zigzag chains which are bridged by qaz creating 2D-sheets. The interwoven infinite sheets are arranged in parallel A···A···A fashion developing 3D-network structure via H-bonds, π–π stacking, and Cu–C contacts. The network structure of 2 exhibits two different copper sites forming two Cu(CN)2 building blocks which are connected by the Ph3Sn groups constructing elongated corrugated chains. The qaz ligand connects these chains forming 3D-network structure containing the rhombic [Cu2(μ3-CN)2] motif. 1 and 2 are luminescent materials which can be used in applications as molecular sensing systems. Also, the catalytic activity of 1 and 2 was investigated towards the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant.

Brown crystals of the MOF [(AgCN) 4 ·(qox) 2 ], 1 were obtained by the reaction of AgNO 3 , quinoxaline (qox) and KCN. The crystal structure of 1 consists of 1D-puckered AgCN chains which are connected by qox molecules forming 2D-fused deformed six-membered rings; [Ag 6 (CN) 4 ·(qox) 2 ] creating wide voids capable to accommodate the qox molecules. 3D-network structure is created via H-bonds, π–π stacking and Ag–Ag interaction. The MOF 1 was tested as corrosion inhibitor for C-steel in 1 M HCl solution using potentiodynamic polarization and electrochemical impedance techniques. Adsorption of the MOF 1 obeyed Langmuir adsorption isotherm. Activation parameters were calculated and discussed.

The reactions of K3[Cu(CN)4], R3SnCl and bipodal ligands, where R = (n-Bu)3SnCl and L = quinoxaline (qox) and R = Me3SnCl and L = quinazoline (qaz) afford the red needle crystals of $$ {}_{\infty }^{3} \left[ {{\text{Cu}}_{2} \left( {\text{CN}} \right)_{2} \mu {\text{-(qox)}}} \right]_{2} $$ , 1 and the orange needle crystals of [Cu2(CN)2μ(qaz)]n, 2. 1 was subjected to single crystals X-ray study while 2 was investigated by IR, 1H NMR and mass spectra as well as TGA. The crystal structure of 1 exhibits puckered CuCN chains connected by qox molecules forming 2D-sheets. The 2D-sheets contain hexagonal nets stacked in A···A···A fashion. The paralleled sheets are close packed via extensive H-bonds, π–π stacking, strong Cu-Cu interaction and short Cu–C contacts which develop 3D-network. Unique rhombic [Cu2(μ3-CN)2] motifs result as consequence of interwoven of the 2D-sheets. The structure of 2 exhibits different XRPD pattern than that of 1 although, the two structures have the same Cu:CN:L stoichiometric ratio. The emission spectra of 1 and 2 display bands around 390, 420 and 475 nm corresponding to MC transition, 1(n,π*) → So and MLCT, respectively. Thus, 1 and 2 can be considered as examples of room-temperature luminescent Cu-containing polymers which can be used in applications as molecular sensing systems. Also, the oxidative degradation of Metanil Yellow (MY) dye has been investigated by hydrogen peroxide catalyzed by 1 or 2. The catalytic activity of 1 is more pronounced than that of 2.

The reactions of K3[Cu(CN)4], R3SnCl (R = Me or ph) and 2,3-dimethyl quinoxaline (dmqox) in H2O/acetonitrile media at room temperature afford the 3D-supramolecular coordination polymers (SCP) $$ ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 2} {\text{dmqox}}} \right] $$ , 1 and $$ ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{dmqox}}} \right] $$ , 2. The structure of the tin free 1 consists of parallel zigzag chains connected by dmqox to form 2D-sheets containing hexagonal 18-atom fused Cu6(CN)4(dmqox)2 rings. The interwoven sheets along the a axis are close packed by extensive H-bonds developing 3D-network structure. The structures of 1 and 2 are investigated by elemental analysis IR, NMR and mass spectra. The ESI+ and ESI− mass spectra of 2 support its polymeric nature while the ESI+ mass spectrum confirms the expected M. W. suggested by elemental analysis. The 13C-NMR spectrum of 2 supports the fact that the network structure of 2 contains the rhombic [Cu2(μ3-CN)2] motif. The structure of 2 was compared with the structure of the reported prototype $$ ^{ 3}_{\infty } \left[ {{\text{Cu}}_{ 2} \left( {\text{CN}} \right)_{ 4} \cdot \left( {{\text{Ph}}_{ 3} {\text{Sn}}} \right)_{ 2} \cdot {\text{qox}}} \right] $$ as well as the other related structures.

Self assembly of K3[Cu(CN)4] with Me3SnCl and quinoxaline (qox) affords the new organotin ternary adduct ∞ 3 [Cu2(CN)3·Me3Sn·qox], 1, as orange platelet crystals. The supramolecular architecture of 1 consists of [Cu2(CN)3]− building blocks connected by the (Me3Sn)+ cations forming infinite corrugated 1D-chains. The chains are bridged by the qox molecules forming 2D-layers containing fused distorted polygons. The layers are interwoven forming 3D-network structure, which are stabilized by close packing effects such as H-bonds as well as Cu···Cu and π–π interactions. IR and mass spectra as well as TGA are investigated.

The reaction of K 3 [Cu(CN) 4 ] in H 2 O with a solution of Ph 3 SnCl and 4-methylpyrimidine (mpym) in acetonitrile affords, at room temperature, the white powder [(Ph 3 Sn) 3 Cu(CN) 4 .mpym·H 2 O], II , precipitating in the mother liquor and colourless platelet crystals [(Ph 3 Sn) 2 Cu(CN) 3 ], I , which was obtained from the filterate after two days. The copper site in I assumes distorted trigonal plane geometry. The network structure of I is constructed via 3D-puckered layers constructed of infinite parallel [CuCN-(μ-Ph 3 Sn)-CN] chains forming waves where the CNSnPh 3 fragments locate the peak and bottom positions of the waves as side arms. The 2D-layers are connected by hydrogen bonds and π–π stacking. This is the first example for a Cu-coordination polymer containing the tetrahedral and bipyramidal configured tin atoms. The pyramidal tetrahedral [Cu(CN) 4 ] 3− anion, in II , are interconnected by two kinds of nanometer spacers; -C N→Sn(Ph 3 )←O(H)H…N C– and –C N→Sn(Ph 3 )–N(mpym)N–Sn(Ph 3 )←N C– creating super-Prussian blue 3D-network structure.

Reaction of Ph3SnCl and K3[Cu(CN)4] with quinoxaline (qox) at room temperature affords the novel 3D-supramolecular coordination polymer (SCP) ∞ 3 [Cu2(CN)4·(Ph3Sn)2·qox], I, as the first example of the organotin-CuCN SCP containing the Ph3Sn fragment. The structure of I displays two Cu(CN)2 building blocks connected by a Ph3Sn cation and qox ligand creating the rhombic [Cu2(μ-CN)2] motif. The structure of I contains three different fused rings, the minicycle [Cu2(μ-CN)2], the 18-atomic [Cu4(Ph3Sn)2(CN)4(qox)2], and the 24-atomic [C8N8Cu4(Ph3Sn)4] rings, which create a non-interpenetrating 3D-network. These rings form a box-like structure with cavities suitable to accommodate bulky phenyl groups. SCP I belongs to the rapidly growing family of supramolecular assemblies containing the quite unusual [Cu2(μ-CN)2] motif, the repeated appearance of which raises the question whether cuprophilic interactions therein are the basic cause of the existence of I.

The reaction of K3[Cu(CN)4], Me3SnCl and 4-methylpyrimidine (mpym) at room temperature affords the 3D-octameric ∞ 3 [Cu8(CN)8(mpym)4], I, in water/acetonitrile and the 3D-host–guest ∞ 3 [Cu8(CN)8(mpym)4 dioxane], II. The X-ray single crystal diffraction of I reveals the formation of homometallic octameric building blocks consisting of three fused 11 membered rings. The 3D-network structure of the supramolecular coordination polymer (SCP), I, consists of two crossing sets of parallel corrugated interpenetrating CuCN chains, which are connected by mpym, hydrogen bonds, π–π stacking and cuprophilic interactions. Species II is isostructural with I as indicated by X-ray powder diffraction and spectroscopic measurements.

The 3D-supramolecular coordination polymer (SCP) (3)∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3⋅Me3Pb⋅qox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated.