Eight silver (I) complexes with P-donor ligands [triphenylphosphine (PPh3), bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,4-bis(diphenylphosphino)butane(dppb)] and mercaptan ligands [3-amino-5-mercapto-1,2,4-triazole (H2AMTA), 2-amino-5-mercapto-1,3,4-thiadiazole (HAMTD), 2-mercapto-6-nitrobenzothiazole (HMNBT) and 2-mercapto-5-methyl-benzimidazole (HMMBD)] named by [Ag2(PPh3)4(HAMTA)2]n (1), [Ag3(dppm)3(AMTD)2]2(BF4)2·(dppm) (2), [Ag3(dppm)3(AMTD)2]2(ClO4)2·(dppm) (3), [Ag4(dppm)4(MNBT)2](SO4)·(H2O) (4), [Ag4(dppe)4(HAMTA)2(AMTA)] (5), [Ag2(dppb)2(HAMTD)2](CF3SO3)2·2(CH3OH) (6), [Ag2(dppb)2(HMNBT)2](CF3SO3)2 (7) and {[Ag(dppb)(HMMBD)2](CF3SO3)·2(CH3OH)·(H2O)}n (8) are characterized by X-ray diffraction, NMR and fluorescence spectroscopy. Complexes 1 and 8 show 2D network structure. Complexes 2–5 are multi-nuclear clusters. Complexes 6–7 are of di-nuclear structure. In complex 7, the offset π⋯π interactions between the neighboring benzene rings help to form the 1-D infinite chain. All the emission peaks of these complexes are attributed to ligands-centered [π–π∗] transitions.The complexes 1–8 with diphosphine ligands and are synthesized and characterized by 31P NMR spectroscopy and fluorescence spectra. Strikingly, complex 1 displays 2D architecture through hydrogen bonds to form network structure. Clusters 3–4 reveal argentophilic interactions. Complex 8 shows 2D network through π-π interaction.Download high-res image (139KB)Download full-size image

Six novel silver(I) complexes with diphosphine ligands, namely [Ag2(μ-dppm)2(phen)2](NO3)2 (1), {[Ag2(dppm)2(μ-bpp)](ClO4)2}n (2), [Ag4(dppm)4(μ-dpe)(CH3CN)2](BF4)4·(H2O)·(CH3CN) (3), {[Ag(μ-dppe)(dicnq)](BF4)·(DMF)}n (4), {[Ag(μ-dppe)(dmapym)](BF4)}n (5) and {[Ag(μ-dppb)(phen)](BF4)·(CH3CN)}n (7) (dppm = bis(diphenylphosphino)methane, dppe = 1,2-bis(diphenylphosphino)ethane, dppb = 1,4-bis(diphenylphosphino)butane, phen = 1,10-phenanthroline, bpp = 1,3-bis(4-pyridyl)propane, dpe = 1,2-di(4-pyridyl)ethene, dicnq = 6,7-dicyanodipyridoquinoxaline, dmapym = 2-amino-4,6-dimethylpyrimidine), were characterized by X-ray diffraction, IR, 1H NMR and fluorescence spectra. These complexes have been synthesized by the reactions of silver salts, diphosphine ligands and various N-donor ligands in different solvents. The complex [Ag2(μ-dppb)2](BF4)2 (6) has been reported in a previous study and complex 7 was prepared by a ring-opening reaction using complex 6 as a precursor. 1H NMR spectroscopy and fluorescence spectra of complex 6 were also measured. Complexes 1 and 6 are dinuclear complexes with an [Ag2(μ-PP)2]2+ ring bridged by diphosphine ligands. In complexes 2, 4, 5 and 7, the Ag ions are bridged by ligands (bpp, dppe and dppb, respectively) to form 1D infinite chain structures. In particular, the [Ag2(dppm)2]2+ units of complex 2 are linked by the bpp ligand rather than the diphosphine ligands. Strikingly, complex 5 displays a 2D “honeycomb” (6,3) network structure formed through hydrogen bonds. Complex 3 consists of a tetranuclear structure where the two [Ag2(μ-dppm)2(CH3CN)]2+ moieties are linked by a dpe ligand in bidentate-bridging fashion. All the emission peaks of these complexes are attributed to ligand-centered [π–π∗] transitions.Complexes 1–7, containing diphosphine ligands, were synthesized and characterized by X-ray diffraction, IR, 1H NMR and fluorescence spectra. Strikingly, complex 5 displays a 2D architecture through hydrogen bonds to form a “honeycomb” (6,3) network structure. Complex 7 is prepared by the ring-opening reaction of complex 6.

The reactions of 1,3-bis(diphenylphosphino)propane (dppp) and 1,10-phenanthroline derivative with Ag salts in the mixed solvent of methanol and dichloromethane generate the corresponding complexes, {[Ag2(dppp)2(phen)2](BF4)2(H2O)2}n (1) (dppp = 1,3-bis(diphenylphosphino)propane), {[Ag2(dppp)2(dmp)2](CF3SO3)2}n (2), {[Ag2(dppp)2(dmp)2](BF4)}n (3) (dmp = neocuproine), {[Ag2(dppp)2(Bphen)2](CF3SO3)2}n (4) and {[Ag2(dppp)2(Bphen)2](ClO4)} (5) (Bphen = 4,7-diphenyl-1,10-diazaphenanthrene). All the complexes are characterized by X-ray diffraction, luminescence, 31P, 1H NMR spectroscopy and terahertz (THz) spectra. These five complexes are of dinuclear structures. The topological analysis of simplified underlying nets reveals that complexes 1–4 have topologically promising architectures formed through hydrogen bonds (F⋯H–C) between the C–H groups of aromatic ring and anions. Thermogravimetric analysis (TGA) shows the complexes 1–5 possess good thermal stability up to 300 °C.Complexes 1–5 with diphosphine ligands were synthesized and characterized by IR, X-ray diffraction, 1H NMR spectroscopy and fluorescence spectra. 1 displays the 2D structure with hydrogen bonds to form networks. 2–4 are of the 3D topology. All emission peaks of 1–5 are exhibited in the solid state at room temperature.

The present work describes the synthesis, full characterization and architectural diversity of six new bioactive silver–organic networks, namely the coordination polymers [Ag(bpa)2(CF3SO3)(H2O)]n (1), {[Ag2(PPh3)2(bpa)2](CF3SO3)}n (2), [Ag(bpe)(CF3SO3)]n (3), [Ag(bpe)(CF3SO3)(CH3CN)]n (4), {[Ag(PPh3)(μ-bpe)]1.5(BF4)}n (5) and [Ag(bpp)(CF3SO3)(CH3CN)2]n (6), which are generated via a mixed-ligand strategy using 1,2-bis(4-pyridyl)ethane (bpa), 1,2-bis(4-pyridyl)ethene (bpe) or 1,3-bis(4-pyridyl)propane (bpp) as the main building block and triphenylphosphine (PPh3) as an ancillary ligand source. Complexes 1–6 were well characterized by IR, 1H and 31P NMR spectroscopy, elemental analysis, fluorescence, THz spectroscopy and single-crystal X-ray crystallography. The complexes 1, 2 and 4–6 have a topological network structure. The type and coordination modes of the bipyridine derivatives and the choice of solvent play a key role in defining the dimensionality as well as the structural and topological features of the resulting networks. Analysis of structures revealed that complex 1 possesses a (54, 62) topological network structure connected through the bridging ligand bpa. Complex 2 has a dinuclear structure and displays a topologically promising architecture connected through hydrogen bonds between the CH groups of aromatic ring and anions. Complexes 3 and 4 possess different 1D infinite chains which are linked by the bridging ligand bpe, and complex 4 can be simplified as having a three-dimensional mesh topology. Complex 5 has a (93, 33) topological network structure connected through the bridging ligand bpe. Like complex 4, complex 6 possesses 1D infinite chains through the bridging ligand bpp, which are linked by hydrogen bonds to form a 3D topological network. Complexes 2 and 4 are generated from CH2Cl2/CH3OH (5:5) and CH3CN respectively, while the other complexes are obtained from CH3CN/H2O (5:5). In addition, complexes 1–6 exhibit interesting fluorescence in the solid state at room temperature.Compounds 1–6 were fully characterized by IR, 1H and 31P NMR spectroscopy, elemental analysis, fluorescence, THz spectra and single-crystal X-ray crystallography. The crystal structures of complexes 1–2, 4–6 consist of topological networks. In addition, complexes 1–6 exhibit interesting fluorescence in the solid state at room temperature.

•Crystal structures and luminescence of five Cu(I) complexes were studied.•Complex 4 is of the infinite zigzag chain that forms by hydrogen bonds N⋯HO.•In complex 5, dppb acts as bridging ligand to form 1D supramolecular structure.•Different anions can regulate and control the emitting colors of complexes 1–5.The mixture of copper(I) salts CuX (X = Cl, Br, SCN, CN, SO3CF3) and 1,10-phenanthroline (phen) reacts with 1,4-bis(diphenylphosphino)butane (dppb) to give dinuclear complexes [Cu2(dppb)(phen)2Cl2]⋅4DMF (1), [Cu2(dppb)(phen)2Br2]⋅DMF (2), [Cu2(dppb)(phen)2(SCN)2] (3) and two 1D chain complexes {[Cu2(dppb)(phen)2(CN)2(H2O)]}n⋅nH2O (4) and {[Cu2(dppb)(phen)2](SO3CF3)2}n (5), respectively. The structures of these compounds were investigated by elemental analysis, single-crystal X-ray diffraction, electronic absorption spectroscopy, fluorescence spectroscopy, 1H NMR and 31P NMR spectroscopy. Each Cu atom adopts a distorted tetrahedral configuration, and all the complexes are considerably air-stable in solid state and in solution. Detailed NMR studies have been performed to disclose the behavior of the prepared copper(I) complexes in solution. All the five complexes are bright green and cyan luminophores in a solid state at room temperature. This makes them potential candidates as cheap emitting materials for electroluminescent devices.

Nine lanthanide complexes with a high L:Ln ratio (4:1), [LnL4](OTf)3 (1–8) (L = tetrakis(O-isopropyl)methylenediphosphonate, OTf = SO3CF3, Ln = Ce, Pr, Nd, Sm, Eu, Gd, Dy, Yb) and [DyL4](OTf)3·DMF (9) have been synthesized through easy and effective methods in air. Each complex was synthesized by the reaction of lanthanide triflate with the L ligand in a solvent mixture (acetonitrile and DMF for 1–8, dichloromethane and DMF for 9). The above complexes, except for complex 9, were synthesized in the presence of 1,10-phenanthroline. The title complexes were characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction analysis, luminescence, NMR spectra and terahertz time-domain spectroscopy (THz-TDS). Structure analysis shows that complexes 1–9 consist of one cation [LnL4]3+ and three triflate anions OTf-. Complexes 1–8 crystallized in the orthorhombic system, space group Pbcn, whereas complex 9 belongs to the space group I222. The cationic [LnL4]3+ fragments in complexes 1–8 are self-assembled to construct 2D layers with a (8·2·8·4) net topology by hydrogen bonding interactions. The OTf− cations in 9 are attached directly to the [DyL4]3+ cations to form a 2-fold hydrogen-bonded three-dimensional (3D) cage structure framework. Solid luminescence of complex 5 displays the characteristic bands of Eu3+, due to a long emission lifetime (4.04 ms of 5D0) and high absolute emission quantum yield (53.30%). Terahertz (THz) time-domain spectroscopy of the complexes was also studied.Nine lanthanide complexes with a high L:Ln ratio (4:1), [LnL4](OTf)3 (1–8) (L = tetrakis(O-isopropyl)methylenediphosphonate, OTf = SO3CF3, Ln = Ce, Pr, Nd, Sm, Eu, Gd, Dy, Yb) and [DyL4](OTf)3·DMF (9) have been synthesized in air. These complexes were characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction analysis, luminescence, NMR spectra and terahertz time-domain spectroscopy (THz-TDS).

The reactions of diphosphine ligands and isoquinoline (i-C9H7N) with Ag salts in the mixed solvent of methanol (MeOH) and dichloromethane (CH2Cl2) generate the complexes [Ag2(dppm)2(NO2)2]·(i-C9H7N)2 (1), [Ag2(dppm)2(i-C9H7N)2(BF4)](BF4) (2), {[Ag(dppe)(i-C9H7N)2](CF3SO3)·(i-C9H7N)}n (3), {[Ag(dppb)(i-C9H7N)2](BF4)2·(i-C9H7N)0.5}n (4) and {[Ag(dppb)(i-C9H7N)(CF3SO3)]·(i-C9H7N)}n (5). These complexes were all characterized by IR, elemental analysis, X-ray diffraction, luminescence, 31P and 1H NMR spectroscopy. Complexes 1 and 2 have dinuclear structures, while complexes 3, 4 and 5 have 1D infinite zigzag chain structures. Complexes 1 and 2 are metal clusters in which there exist Ag⋯Ag metal bonds, whilst in compounds 3, 4 and 5, two silver atoms are bridged by the diphosphine ligands to form the 1D infinite zigzag chains. Complexes 3 and 5 are 2D topologically promising architectures and complex 4 is a 3D topologically promising architecture. In addition, complexes 1–5 exhibit interesting fluorescence in the solid state at room temperature. At the same time, we also studied the terahertz spectra of the complexes, which show more accurate characteristics of each group of complex.The crystal packing of all five complexes shows that 1D infinite chains are self-assembled to construct the 2D or 3D supramolecular networks by hydrogen bonding. The choice of inorganic counter anions and co-ligands has great influence on the experimental results and terahertz spectra.

Seven lanthanide–organic frameworks [(CeCl2L(phen))2(μ-Cl)2]·CH3CN (1) (L = tetrakis(O-isopropyl)methylenediphosphonate, phen = 1,10-phenanthroline) and [LnCl(H2O)3L(phen)]·nCH3CN (n = 0 for 2, n = 2 for 3, n = 1.5 for 4, n = 0 for 5, n = 1.5 for 6, n = 1.5 for 7) (Ln = Dy, Ho, Er, Tm, Yb, Lu for 2–7, respectively) have been synthesized by the reaction of lanthanide chlorides, the ligand L and phen in acetonitrile at room temperature. These title complexes were characterized by IR, elemental analyses, single-crystal X-ray diffraction analysis, luminescence, thermal analysis, 1H NMR and 31P NMR spectroscopy. The complex [(CeCl2Lphen)2(μ-Cl)2]·CH3CN (1) is a dinuclear compound and displays a two-dimensional mesh 63 topology formed by π–π interactions. Complexes 2–7 can be simplified as having a two-dimensional mesh 4.82 topology formed by hydrogen bonds (C–H⋯Cl and O–H⋯Cl). These interesting structures are rarely found. We found a fluorescence quenching phenomenon which may be due to the presence of crystalline water molecules and solvent. Their terahertz (THz) time-domain spectroscopy was also studied.We have investigated two kinds of interesting topologies (two-dimensional mesh 63 topology and two-dimensional mesh 4.82 topology) and their terahertz (THz) time-domain spectra.

Reaction of transition metal(II) salts with 2,2′-biimidazole (H2biim) and co-ligands formed a series of new complexes, [M(H2biim)2(bipy)2](NO3)2·2H2O (1–3) (M = Co, Ni, Zn), [Co(H2biim)2(bipy)](ClO4)2·3H2O (4), {[Cu(H2biim)2]3(μ-C3H3O4)2 (C3H2O4)2}·6H2O (5), [Co(H2biim)2(H2O)2](C3H3O4)2 (6) (bipy = 4,4′-bipyridine, C3H2O4 = malonate dianion, C3H3O4 = malonate anion). These complexes were characterized by single-crystal X-ray diffraction, and elemental analysis. All complexes except 4 were also characterized by luminescence spectra and thermogravimetric analysis. The crystal packing of these six complexes shows that cationic M(II)(2,2′-biimidazole) fragments are self-assembled to construct the 3D supramolecular networks by hydrogen bonding and π–π interactions. The 3D supramolecular networks are significantly affected by counter anion and co-ligands. In complexes 1–3, there are two sets of (4,4) nets which pass through each other to form inclined 2D interpenetration. Complex 4 is obtained by similar reactions as 1 Compared with 1, the only difference in 4 with the reactant Co(NO3)2·6H2O replaced by Co(ClO4)2·6H2O, but it has a very different structure. In 4, the 3D networks containing cavities of 23 × 23 Å is formed. In complex 5, the uncoordinated waters form an infinite 1D pipe structure which is embedded in the 3D porous network. The acid–water ring and R22(9) synthons in complex 6 lead to the formation of (4,4) 2D network.The crystal packing of all six complexes shows that cationic M(II)(2,2′-biimidazole) fragments are self-assembled to construct the 3D supramolecular networks by hydrogen bonding and π–π interactions. The choice of inorganic counter anions and co-ligands has great influence on the experimental productions.

Eight silver(I) complexes containing DPEphos (bis[2-(diphenylphosphino)phenyl]ether) and dppe (bis(diphenylphosphino)ethane), namely [Ag2Cl2(DPEphos)2(dppe)](CH3OH)2(DMF) (1), [Ag2Br2(DPEphos)2](DMF)2 (2), [Ag2(OTf)2(DPEphos)2(dppe)] (3) (OTf = trifluoromethanesulfonate), [Ag2(NO3)2(DPEphos)2(dppe)] (4), [Ag(DPEphos)(dppe)](OTf) (5), [Ag(NO3)(DPEphos)] (6), [Ag(NO2)(DPEphos)] (7) and [Ag(DPEphos)(dppe)](BF4) (8), have been synthesized. They were characterized by IR spectroscopy, X-ray diffraction, RT luminescence, 1H and 31P NMR spectroscopy. Complexes 5–8 were obtained in the mixed solvents of CH3OH and CH2Cl2, while 1–4 were obtained in the mixed solvents of CH3OH, CH2Cl2 and DMF (DMF = N,N-dimethylformamide). Complexes 1–4 display dinuclear structures, in which two silver atoms are bridged by one dppe ligand (for 1, 3 and 4) or two Br atoms (for 2). The other four are mononuclear complexes. The 31P NMR spectra of the title compounds are measured, each spectrum shows rich signals which belong to P atoms in different chemical environment. In the 31P NMR spectra, there exist splitting signals (doublets or triplets) which can be attributed to the coupling of the 107,109Ag–31P or 19F–31P, where the coupling of 19F–31P was found for the first time in silver(I)–P complexes containing OTf− or BF4− anions.Eight new Ag(I) complexes with bis[2-(diphenylphosphino)phenyl]ether (DPEphos) and bis(diphenylphosphino)ethane (dppe) have been synthesized and characterized by elemental analysis, X-ray diffraction, RT luminescence, 1H NMR and 31P NMR spectroscopy.

The reactions of triphenylphosphine (PPh3) and 4,4′-bipyridine (bipy), 1,2-di(4-pyridyl)ethane (dpa), 1,3-bis(4-pyridyl)propane (bpp) ligands with AgX (X = BF4 and NO2) lead to five new complexes: {[Ag(PPh3)2(bpp)](BF4)}n (1), [Ag(dpa)(BF4)]n (2), {[Ag(PPh3)2(μ-bipy)]2(BF4)2}n(3) and {[Ag(PPh3)2(CH3CN)]2(μ-bipy)}(BF4)2(4) and [Ag(dpa)(NO2)]n (5). In 1, 2 and 3, the Ag atoms are bridged by pyridyl-containing ligands (bpp, dpa and bipy, respectively) to form infinite chain structure. In 4, the Ag atoms are bridged by bipyridine to form a dinuclear structure. Complex 5 is of layer structure which is formed by silver atoms, oxygen atoms from NO2− and dpa. All the complexes are characterized by X-ray diffraction, fluorescence and 1H NMR spectroscopy.Five silver(I) complexes based on rigid and flexible pyridyl-containing ligands have been synthesized and characterized by elemental analysis, X-ray diffraction, 1H NMR and fluorescence spectroscopy.

Five new copper(I) complexes containing PPh3 and C16H6N6, [Cu(PPh3)(C16H6N6)Cl]·H2O (1), [Cu(PPh3)(C16H6N6)Br]·CH3CN (2), [Cu(PPh3)(C16H6N6)I]·CH3CN (3), [Cu(PPh3)(C16H6N6)(CN)]·0.5 CH2Cl2(4) and Cu(PPh3)(C16H6N6)(SCN) (5) {PPh3 = triphenylphosphine, C16H6N6 = [2,3-f]-pyrazino-[1,10] phenanthroline-2,3-dicarbonitrile} have been synthesized for the first time. These complexes are obtained by the reactions of CuX (X = Cl, Br, I, CN, SCN) with the bidentate ligand C16H6N6 and the monodentate ligand PPh3 in the molar ratio of 1:1:1 in the mixed solvent of CH2Cl2 and CH3CN(5 ml/5 ml). They are characterized by X-ray crystallography, luminescence, IR, 1H NMR and 31P NMR. In solid state the complexes 1–5 are mononuclear with similar structures, but in solution they have different structures according to their different 1H NMR signals. All the complexes exhibit intense luminescence in solid state at room temperature.Five copper(I) complexes containing PPh3 and C16H6N6, {PPh3 = triphenylphophine, C16H6N6 = [2,3-f]-pyrazino-[1,10] phenanthroline-2,3-dicarbonitrile} have been synthesized for the first time. 1–5 are characterized by X-ray crystallography, luminescence, 1H and 31P NMR. 1–5 in the solid state exhibit intense luminescence at room temperature.Highlights► Five Copper (I) complexes of [2,3-f]-pyrazino-1,10-phenanthroline-2,3-dicarbonitrile are reported. ► The coordination chemistry of C16H6N6 is interesting. ► 1–5 exhibit intense luminescence peaks around 450 nm in solid state. ► The intensity of the emission peaks is increased because of the ligand C16H6N6. ► The 1H and 31P NMR spectra of 1–5 are dependent on the counter anion.

By the reaction of [Ag3(dppm)3I2]I with (NH4)2WS4 in MeCN/DMF (1:1), a trigonal bipyramid-shaped cluster [Ag3 I (dppm)2 WS4] (1) was isolated [dppm = bis (diphenylphosphino) methane]. By the reaction of (NH4)2WS4 with AgSCN and dppm in MeCN/DMF (1:1) in the presence of 1,10-phenathroline, an insect-shaped cluster [Ag4 (SCN)2 (dppm)4WS4]·H2O (2) was synthesized. Compounds 1 and 2 were characterized by single-crystal X-ray diffraction, luminescence, IR, UV–Vis, 1H and 31P NMR spectroscopy. In 1, WS42- and μ3-I are coordinated to three Ag atoms, which are further bridged by two dppm ligands. In 2, Ag1 and Ag4 are coordinated by two P atoms from two dppm ligands, one μ3-S from WS42- and one S atom from SCN− while Ag2 and Ag3 are coordinated by one μ2-S atom and one μ3-S atom from WS42-, two P atoms from two dppm ligands.Graphical abstractTwo new W–Ag–S clusters are synthesized. In the trigonal bipyramid-shaped cluster [Ag3 I (dppm)2 WS4], one WS42-, one I− and two dppm ligands are coordinated to three Ag atoms. In the insect-shaped cluster [Ag4 (SCN)2 (dppm)4WS4]·H2O, four Ag atoms are coordinated by one WS42-, two SCN− and two dppm ligands.Research highlights► A novel cluster [Ag3I(dppm)2 WS4] (1) was prepared by substitution reaction, a new cluster [Ag4(SCN)2 (dppm)4 WS4]·H2O (2) was synthesized by ‘one-pot’ reaction. ► In synthesis of cluster 2, 1,10-phenathroline(phen) acts as catalysis. ► The coexistence of coordinated anion (SCN− or I−) and bridging dppm ligand help to form span-new frameworks in clusters 1–2 which are beyond the fourteen fundamental skeletons founded for mono-M′ clusters.

Under the catalysis of 1,10-phenathroline (phen), (NH4)2 M'S4 (M’ = Mo,W) reacts with CuSCN and dppm in mixed solvent MeCN/DMF (1:1) to yield two saddle-shaped clusters [WS4Cu4(SCN)2 (dppm)3]·3DMF·2CH3CN (1) and [MoS4Cu4(SCN)2 (dppm)3]·4DMF (2) (dppm = bis (diphenylphosphino) methane). Compounds 1–2 were characterized by elemental analysis, IR, UV–Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction. Each [M'S4]2− (M’ = Mo, W) anion coordinates to four Cu atoms through four bridging S atoms, and all S atoms are coordinated with two Cu atoms. In each cluster the four Cu atoms are almost in one plane, and the M’ atom is above the plane. Cluster 1 was characterized by luminescent with the λem = 545 nm. The possible catalysis mechanism of phenathroline is discussed.Under the catalysis of 1,10-phenathroline, (NH4)2 M'S4 (M’ = Mo,W) reacts with CuSCN and dppm in MeCN/DMF (1:1) mixed solvent to yield two saddle–shaped clusters [WS4Cu4(SCN)2 (dppm)3 ]·3DMF·2CH3CN (1) and [MoS4Cu4(SCN)2 (dppm)3]·4DMF (2) (dppm = bis (diphenylphosphino) methane). Compounds 1–2 were characterized by IR, UV–Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction.Highlights► Under the catalysis of 1,10-phenathroline (phen), two clusters [M'S4Cu4(SCN)2 (dppm)3 ] (M' = Mo, W) were synthesized. ► The method using phen as the catalysis was confirmed to be an effective strategy of synthesizing new metal clusters. ► The possible catalysis mechanism of phenathroline is discussed. ► The skeletons of Mo/W-Cu/Ag clusters are affected by the coordinated anions and the coordination number of metal atom.

Two new compounds (H3biim)(NO3)(1) and (H4biim)(phthgly)2 (2) (H2biim=biimidazole; Hphthgly=N-phthaloylglycine) have been synthesized and characterized by luminescence and single crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group C2/c, where a = 14.8078(15), b = 5.9233(6), c = 20.028(2) Å, β = 92.7910(10)°, V = 1754.6(3) Å3 and Z = 8. Compound 2 crystallizes in the monoclinic space group P2(1)/n, where a = 15.3775(14), b = 5.3200(6), c = 6.4689(18)Å, β = 115.418(2)° V = 1216.9(2)Å3 and Z = 4. In 1, the N–H groups of H3biim+ and the oxygen atoms of NO3− are linked by hydrogen bonds leading to H3biim+(N,N)–R22(10) and N–H···O interactions forming infinite 1D helical chains along the b-axis. Compound 2 consists of a planar diprotonated biimidazole moiety and two phthgly anions which connect to the dication by hydrogen bonds phthgly−(O,O)–R22(9).

Two new silver(I) complexes containing dppm, nitrogen heterocyclic ligands and sulfate anions, namely [Ag2(μ-dppm)2(μ-SO4)(2-amp)2]·CH3OH (1) and [Ag4(μ-dppm)2(μ-SO4)2(μ-4,4′-bpy)2]·2CH3OH (2) (dppm = bis(diphenylphosphino)methane, 2-amp = 2-aminopyrimidine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized by IR, X-ray crystallography, luminescence, 1H, 31P NMR spectroscopy. In complex 1, [Ag2(μ-dppm)(μ-SO4)(2-amp)2] binuclear units are linked through robust hydrogen-bond synthon R22(8) to give rise to a 1D polymer. While in complex 2, two [Ag2(μ-dppm)(μ-SO4)] units are linked together to form a tetranuclear cluster by two 4,4′-bipyridine ligands.Two new silver(I) complexes, namely [Ag2(μ-dppm)2(μ-SO4)(2-amp)2]·CH3OH (1) and [Ag4(μ-dppm)2(μ-SO4)2(μ-4,4′-bpy)2]·2CH3OH (2) (dppm = bis(diphenyphosphino)menthane, 2-amp = 2-aminopyrimidine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized. Complex 1 is a 1D polymer, while complex 2 is a tetranuclear cluster.

At ambient temperature, two silver(I) complexes [Ag4(SO4)2(dppm)4]·5CH3CH2OH·1/2H2O (1) and [Ag2(SO4)(dppm)2(2-ampz)]·CH3OH·H2O (2) (dppm = bis(diphenylphosphino)methane, 2-ampz = 2-aminopyrazine) were obtained by the reaction of Ag2SO4 with dppm in the presence of pyrazine or 2-aminopyrazine. They are characterized by IR, X-ray crystallography, luminescence and 1H, 31P NMR spectroscopy. Complex 1 is a tetranuclear cluster. In complex 2, the units [Ag2(SO4)(dppm)2] are connected by 2-aminopyrazine to form a 1D linear polymer. Due to the subtle interactions of different nitrogen heterocyclic ligands with silver ions, two SO42− anions in 1 adopt μ3-O, O′, O′ and unique μ4-O, O, O′, O′ bonding modes respectively, while SO42− anion in 2 adopts μ-O, O′ bonding mode.Two new Ag2SO4-dppm complexes have been synthesized. Due to the subtle interactions of different nitrogen heterocyclic ligands with silver ions, two SO42− anions in 1 adopt μ3-O, O′, O′ and unique μ4-O, O, O′, O′ bonding modes respectively, while SO42− anion in 2 adopts μ-O, O′ bonding mode.

Complexes [Zn(NCS)2(2-AMP)2] (2-AMP = 2-aminopyrimidine) 1 and [Cd(SCN)2(2-AMP)2]n2 are prepared and characterized by X-ray crystallographic methods. 1 crystallizes in the monoclinic, space group C2/c, with a = 13.5761(14), b = 8.3330(10), c = 13.5962(15) Å, β = 99.5450(10)°, V = 1516.8(3) Å3, Z = 4. In 1, the zinc atom is coordinated by four N atoms from two AMP and two NCS−. 2 crystallizes in the monoclinic, space group C2/c, with a = 9.7259(11), b = 19.332(2), c = 8.2149(9) Å, β = 99.817(2)°, V = 1522.0(3) Å3, Z = 4. Complex 2 is made up of 1D chains along a-axis. Each Cd is attached to four NCS− bridges and two pendant 2-AMP ligands.

Isomeric polymers [Cd2(mbt)4]n and [Cd(mbt)2]n (mbt = mercaptobenzothiazole) are investigated. The complex {[Cd(μ-η2-C7H4NS2)2][Cd(μ-η2-C7H4NS2) (μ-η3-C7H4NS2)]}n is formed by the reaction of Cd(NO3)2·4H2O with 2-Hmbt in the presence of H2biim in EtOH/H2O. The complex crystallizes in the orthorhombic space group Pca2(1), where a = 21.892(2), b = 9.8994(11), c = 14.8687(15) Å, α = 90, β = 90, γ = 90º, V = 3,222.3(6) Å3, and Z = 4. The two Cd atoms, one exhibits a CdN2S2 tetrahedral geometry and the other exhibits a distorted CdN2S3 trigonal bipyramidal geometry, are linked by bridging–chelating mbt and bridging mbt ligands.

Two pyrazine-connected 1D copper(I) dppm polymers, {[Cu3(dppm)3Br2][Cu2(dppm)(pyz)Br2] Br · (CH3OH)2}n (1) and {[Cu2(dppm)2(NO3)2(pyz)](pyz)}n (2) (dppm = bis(diphenylphosphino)methane, pyz = pyrazine) have been synthesized and characterized by X-ray crystallography, luminescence, IR, 1H, and 31P NMR. Structure analysis shows that complex 1 is a neutral 1D polymer in sine-curve-like form, while complex 2 is in linear form. And photoluminescent study of them shows that they exhibit fluorescent emission bands at ca. 434 nm and 431 nm, respectively.Two 1D pyrazine-connected copper(I)-dppm polymers were synthesized; And interestingly, one is in sine-curve-like form while the other is in straight-like form.

At ambient temperature, three 1D nitrogen-heterocyclic Cu(I)-diphosphine polymers, {[Cu2(dppm)2(BF4)2(pyz)](CH2Cl2)2}n (1), {[Cu2(dppm)2(4,4′-bpy)(CF3SO3)](CF3SO3)(CH3OH)}n (2), {[Cu2(dppe)2 (phen)2](ClO4)2(CH2Cl2)}n (3) (dppm = bis(diphenylphosphino)methane, dppe = bis(diphenylphosphino)ethane, pyz = pyrazine, 4,4′-bpy = 4,4′-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by X-ray crystallography, luminescence, IR, 1H, and 31P NMR. Structure analysis shows that 1 is a 1D linear polymer, 2 is a 1D stair-shaped polymer, and 3 is a 1D W-shaped polymer. A photoluminescent study of them shows that they exhibit fluorescent emission bands at ca. 555 nm, 535 nm and 557 nm, respectively.Three 1D nitrogen-heterocyclic copper(I) diphosphine polymers were synthesized. And interestingly, one is in linear form, one is in stair-shaped form, while another is in W-shaped form.