Inorganic Chemistry Communications (v.14, #10)

Contents List (iii-xi).

A macrocyclic ligand 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo-[b,i][1,4,8,11]tetraazacyclotetradecine and its nickel(II) complex: Syntheses, reaction mechanism and structures by Xuan Shen; Lu Sun; Bo-Kun Jiang; Xin Wang; Akio Nakashima; Naoki Miyamoto; Kazunori Sakata; Yan Xu; Dun-Ru Zhu (1555-1560).
The template reaction of o-phenylenediamine, 1-benzoylacetone and nickelous acetate tetrahydrate results in two structure isomers, 6,17-dimethyl-8,15-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel (II) (2) and 6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel (II) (4). However, the latter has been neglected in the previous research because of its low yield in the template reaction. The mechanism of this template reaction is discussed. Though the steric hindrance between the phenyl ring and the benzo ring in 2 is greater than that in 4, the intermediate of the former shows better structural stability than that of the latter, leading to obviously higher final yield of 2 compared with that of 4. n-Butyl alcohol is used artfully to separate the crude product of the template reaction into almost pure 2 and a mixture of 2 and 4 in a mole ratio of 1:5. The free base of 2, 5,14-dihydro-6,17-dimethyl-8,15-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (1), can be synthesized by demetalization of 2 with gaseous HCl. The same treatment to the mixture of 2 and 4 in a mole ratio of 1:5 leads to the free base of 4, 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (3). The neglected macrocyclic compounds 3 and 4 have been characterized unambiguously and their single-crystal structures have also been determined by X-ray diffraction analysis for the first time.A macrocyclic ligand 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine and its nickel(II) complex, 6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel (II), have been synthesized and characterized unambiguously. Their single-crystal structures have also been determined by X-ray diffraction analysis for the first time.Display Omitted► A template reaction results in a mixture of (E)-Nidmdptaa and (Z)-Nidmdptaa. ► (E)-Nidmdptaa and (Z)-Nidmdptaa are macrocyclic structure isomers. ► (E)-Nidmdptaa is successfully separated from the mixture of isomers. ► (E)-H2dmdptaa, the free base of (E)-Nidmdptaa, is synthesized and characterized. ► The single-crystal structures of (E)-Nidmdptaa and (E)-H2dmdptaa are determined.
Keywords: Template reaction; Structure isomer; Reaction mechanism; Macrocyclic compound; Single-crystal structure;

The oxidation of benzyl alcohols has been studied in the presence of isobutyraldehyde as co-catalyst, molecular oxygen as oxidant and copper (II) meso-tetra phenyl porphyrin (CuTPP) as catalyst. The CuTPP catalyst exhibits good activity and high selectivity under mild conditions. The effects of temperature and solvents have also been investigated in this catalyst system.The oxidation of benzyl alcohols has been studied in the presence of isobutyraldehyde as co-catalyst, molecular oxygen as oxidant and copper (II) meso-tetra phenyl porphyrin (CuTPP) as catalyst. The CuTPP catalyst exhibits good activity and high selectivity under mild conditions. The effects of temperature and solvents also have been investigated in this catalyst system.Display Omitted► Homogeneous oxidation of benzyl alcohols has been done under atmospheric pressure of oxygen. ► The electronic effect of the substituents in the benzyl alcohols and reaction behavior has been compared. ► Also it was found that the yield of reaction was rather low in the absence of the catalyst.
Keywords: Cytochrome P-450; Copper (II) tetra phenyl porphyrin; Benzyl alcohols; Molecular oxygen; Isobutyraldehyde; Oxidation;

Salicylaldehyde 2-phenylquinoline-4-carboylhydrazone (H2L), and its novel tetranuclear cobalt(II), nickel(II) complexes have been synthesized and characterized. The crystal structure of (NiL)2·[NiL(H2O)(DMF)]2·H2O·DMF obtained from DMF solutions of compound 2 was determined by X-ray diffraction analysis. The DNA-binding investigation suggests that the two complexes bind to DNA via groove binding mode. The in vitro antibacterial activity of complexes against Escherichia coli, Staphylococcus aureus, Bacillus subtilis was screened and compared to the activity of the free ligand, the antibacterial activity of complex 1 is active than complex 2 which is in consistent with their DNA-binding behaviors.Two novel tetranuclear cobalt(II), nickel(II) complexes have been synthesized and evaluated for their DNA-binding and antibacterial activity against Escherichia coli, Staphylococcus aureus and Bacillus subtilis. Display Omitted► Two novel tetranuclear complexes were synthesized and characterized. ► The complexes interact with CT-DNA via groove binding mode. ► The antibacterial activity of complex 1 is active than complex 2.
Keywords: Salicylaldehyde 2-phenylquinoline-4-carboylhydrazone; Tetranuclear complex; Groove binding; Antibacterial activity;

This paper reports a facile synthesis for monodisperse palladium nanosphere with the diameter of 200 nm in the mixture solution of dimethyl sulfoxide (DMSO) and ethanol without using any other capping agent. It was found that the ratio of DMSO to ethanol is a key parameter in size and shape control. The as-prepared product in this report exhibit prominent catalytic activities in Suzuki coupling reactions and can be reused at least five times without loss of catalytic activity.A facile synthesis of palladium nanosphere with 200 nm in size at room temperature without employing any template or capping agent; and the as-prepared product exhibit prominent catalytic activities in Suzuki cross coupling reactions and can be reused at least five times without loss of catalytic activity.Display Omitted► Monodisperse Pd nanospheres were obtained by a one-step reaction. ► The as-produced samples exhibit prominent catalytic activities in Suzuki reaction. ► Pd nanospheres can be reused five times without loss of catalytic activity.
Keywords: Palladium; Nanosphere; Catalysis; Suzuki reaction;

‘One-pot’ synthesis of two molybdenum/tungsten (VI)–copper(I) mixed metal clusters under catalysis of 1,10-phenathroline by Qiong-Hua Jin; Ye-Lan Xiao; Ke-Yi Hu; Zhong-Feng Li; Rong Wang; Cun-Lin Zhang (1579-1583).
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 12 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 12 were characterized by IR, UV–Vis, 1H NMR, 31P NMR, and single-crystal X-ray diffraction.Display Omitted► 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.
Keywords: Cluster; Bis (diphenylphosphino) methane; Molybdenum (VI); Tungsten(VI); Copper (I); Phenathroline;

Hydrothermal reaction of Zn(II) acetate, 4,4′-bipyridyl (bpy) and 1,2,3-benzenetricarboxylic acid (H3bta) results in a 3-D coordination framework {[Zn4(bta)2(Hbta)(bpy)3](H2O)3} n (1), which shows the self-penetrating net with a new 4-connected topological prototype and chiral helical character.Hydrothermal reaction of Zn(II) acetate, 4,4′-bipyridyl (bipy) and 1,2,3-benzenetricarboxylic acid (H3bta) results in a 3-D coordination framework, which shows the self-penetrating net with a new 4-connected topological prototype and chiral helical character.Display Omitted► A self-penetrating 4-connected coordination framework with chiral helical features from Zn(II) and mixed organic ligands of H3bta and bipy. ► Complex 1 represents a unique self-penetrating supramolecular pattern with the unprecedented (4.62.83)2(42.62.82) net topology. ► Homochiral crystalline packing of right-handed or left-handed helices was found in the title complex.
Keywords: 1,2,3-Benzenetricarboxylic acid; Hydrothermal synthesis; 4-connected topological prototype; Chiral helical character;

A microporous [Ni33-OH)] cluster-based framework with 9-connected ncb topology by E. Yang; Zi-Sheng Liu; Shen Lin; Shun-Yu Chen (1588-1590).
A porous metal organic framework [NiIIINiII 2(μ 3-OH)(bdc)1.5(int)3] n x(solvents) (1: bdc = 1,4-benzenedicarboxylate; int = isonicotinate) based on the trinuclear Ni3(μ 3-OH) units was solvothermally synthesized and structurally characterized. It features a three-dimensional 9-connected ncb-type framework with two kinds of cage substructures and large one-dimensional channels. Both N2 and CO2 gas sorption studies of 1 were investigated to demonstrate the permanent porosity in 1.A microporous metal organic framework with 9-connected ncb topology is constructed from the trinuclear Ni3(μ 3-OH) units and shows gas sorption properties.Display Omitted► Synthesis and structure of a microporous [Ni33-OH)] cluster-based framework ► Nine-connected ncb topology in metal organic framework ► A microporous metal organic framework with N2 and CO2 gas sorption properties
Keywords: Solvothermal synthesis; Isonicotinate; Topology; Crystal structure; Gas sorption;

In this study, a novel dinuclear Ag(I)-pyridine-2,3-dicarboxylate complex with 1,3-diaminopropane ligand (pda), [Ag2(μ-2,3-pydc)2(Hpda)2]⋅2H2O (H22,3-pydc = pyridine-2,3-dicarboxylic acid), has been synthesized. The molecular structure of complex has been determined by the single crystal X-ray diffraction. The complex has been observed to crystallize in the triclinic space group P-1. The Ag(I) ion exhibits a distorted trigonal pyramidal geometry by two 2,3-pydc and one protonated monodentate Hpda ligands. The 2,3-pydc ligand acts as a tridentate bridging ligand with a new coordination mode between two Ag(I) centers through the pyridine N and carboxyl μ-O atoms, forming a 4-membered parallelogram Ag2O2 ring. The most striking feature is that the structure contains both intra- and inter-molecular C―H···Ag hydrogen bonding interactions to form infinite 1D chains containing R 2 2(8) rings.In this study, a novel dinuclear Ag(I)-pyridine-2,3-dicarboxylate complex with 1,3-diaminopropane ligand (pen), [Ag2(μ-2,3-pydc)2(Hpda)2]⋅2H2O (H22,3-pydc = pyridine-2,3-dicarboxylic acid), has been synthesized. At this complex, both intra-molecular anagostic and inter-molecular multicenter hetero-acceptor hydrogen bond (IMH) M―H―C interactions are determined with X-ray crystallography techniques.Display Omitted► The pydc ligand acts as a tridentate bridging ligand with a new coordination mode between two Ag(I) centers through the pyridine N and carboxyl μ-O atoms, forming a 4-membered parallelogram Ag2O2 ring. ► For this complex, both intra-molecular anagostic and inter-molecular multicentre hetero-acceptor hydrogen bond (IMH) M–H–C interactions are determined by using X-rays crystallography techniques. ► The complex exhibits red photoluminescence in the solid state at room temperature with emission maximum at 483 nm upon excitation at 310 nm.
Keywords: Pyridine-2,3-dicarboxylate complex; Silver(I) complex; Dinuclear complex; 1,3-diaminopropane; C―H···Ag interactions;

Dual chemosensing properties of new ferrocene-based receptors towards fluoride and copper(II) ions by Soosai Devaraj; Veeramuthu Stalin Elanchezhian; Muthusamy Kandaswamy (1596-1601).
The new ferrocene based receptors N-[4-ferrocenyl-2-methyl-4-oxobut-1-enyl]-N′-phenylthiourea (1), N-[4-ferrocenyl-2-methyl-4-oxobut-1-enyl]-N′-[4-nitrophenyl]thiourea (2) were synthesized and characterized. Fluorescence titrations of receptors 1 and 2 with various transition metal ions showed selective response to Cu2+ ions and the emission intensities quenched significantly. Electrochemical titrations with anions revealed that receptors 1 and 2 sensed the F anion in high selectivity with a cathodic shift of 100 mV.Two new colorimetric chemosensors 1 and 2 have been synthesized and characterized by different spectroscopic techniques like IR, Mass and NMR. Anion binding studies carried out using UV–visible spectrophotometric titrations revealed that these receptors exhibit selective recognition towards F over other halide anions. Chromogenic receptors 1 and 2 undergo distinct color changes from yellow to green (1) and red to dark green (2) on gradual addition of Cu(II) and can be used as colorimetric probes for spectrophotometric and visual analysis of Cu(II) in the presence of other transition metal ions such as Mg2+, Ca2+, Cd2+, Ni2+, Co2+, Mn2+ and Zn2+. Fluorescence titrations of receptors 1 and 2 with various transition metal ions showed selective response to Cu2+ ions and the emission intensities quenched significantly. Electrochemical titrations with anions revealed that receptors 1 and 2 sensed the F anion in high selectivity with a cathodic shift of 100 mV.Display Omitted► Easy to synthesize 1 and 2. ► Detectable by using colorimetric, optical (UV–vis and fluorescence) and electrochemical methods. ► Both sensors highly sensitive at low analyte concentration. ► These receptors can also be used to detect copper ions.
Keywords: Chemosensor; Ferrocene; Cationic sensor; Anionic sensor; Electrochemical studies;

Assembly of a water-insoluble strontium metal–organic framework with luminescent properties by Sheng-Han Lo; Hsin-Kuan Liu; Jun-Xiang Zhan; Wei-Cheng Lin; Ching-Che Kao; Chia-Her Lin; Vítězslav Zima (1602-1605).
A new strontium metal–organic framework, [Sr2(BTEC)(H2O)4]∙2H2O (1) (H4BTEC = benzene-1,2,4,5-tetracarboxylic acid), has been successfully synthesized by mixing the starting reagents. The single-crystal structure analysis showed that compound 1 displayed three-dimensional structures containing inorganic motifs with two-dimensional layers pillar-connected through organic linkers and forming water-coordinated neutral framework. Further studies revealed that compound 1 was insoluble in water and that it emitted strong luminescence at approximately 437 nm after dehydration.A new strontium metal-organic framework was synthesized by mixing the starting. The extended 3D framework contains two-dimensional inorganic layers connected through organic linkers and forming neutral frameworks.Display Omitted► A new strontium metal-organic framework was synthesized by mixing the starting reagents. ► Strontium metal-organic framework is an extended 3D framework. ► Strontium metal-organic framework is insoluble in water. ► Strontium metal-organic framework emits strong luminescence at around 437 nm after dehydration.
Keywords: Strontium complex; Metal–organic framework; Luminescent; Water-insoluble;

Diethyl-2,2′-biquinoline-4,4′-dicarboxylate (debq) reacts with pentacarbonylbromorhenium in toluene to give fac-[Re(CO) 3 (debq)Br]; subsequent reaction with AgOTf in MeCN affords the cationic complex fac-[Re(CO) 3 (debq)(MeCN)]OTf. X-ray crystallographic data on fac-[Re(CO) 3 (debq)Br] show that the debq ligand is coordinated in a bidentate fashion at an angle of 32° from the equatorial plane of the complex: DFT calculations confirm this as the lowest energy conformation. fac-[Re(CO) 3 (debq)Br] and fac-[Re(CO) 3 (debq)(MeCN)]OTf both possess 1 MLCT absorptions in the visible region, the former most red-shifted to ca. 465 nm. Both complexes demonstrated unusual luminescent properties: in solution, emission appears to be dominated by ligand-centred processes, whereas only 3 MLCT emission, tailing into the near-IR, was observed in the solid state at 671 (τ = 59 ns) and 711 nm (τ = 19 ns) for fac-[Re(CO) 3 (debq)(MeCN)]OTf and fac-[Re(CO) 3 (debq)Br], respectively. However, the debq ligand is not labile in these complexes, which are robust to competing ligands and coordinating solvents.The development of rhenium complexes based on the substituted 2,2′‐biquinoline core represent a useful and viable avenue towards kinetically stable species with tunable emission properties towards the near-IR region.Display Omitted► The debq ligand is coordinated to Re at an angle of 32° from the equatorial plane. ► Complexes possess 1 MLCT absorptions at 400–450 nm. ► 3MLCT emission, tailing into the near-IR, observed in the solid state. ► Complexes are stable to competing ligands and coordinating solvent.
Keywords: Rhenium; 2,2′-biquinoline; Luminescence; Density functional theory; Near-IR;

A new bimetallic complex [HNEt3][Cuq2IEu(hfac)3] (q = 8-hydroxyquinolinato, hfac = hexafluoroacetylacetonate) was prepared simply with only one step and characterized. Upon excitation of the organic ligand q, the sensitized europium luminescence was achieved.A new bimetallic complex [HNEt3][Cuq2IEu(hfac)3] was prepared simply with only one step. Irradiating of [n → π*] absorption of q, lights up the EuIII luminescence through an antenna effect.Display Omitted► Efficient lanthanide emission is usually achieved by metallic fragment as sensitizer. ► Generally, such d–f hybrid complex was synthesized multi-stepwise. ► Now analogous complex [HNEt3][Cuq2IEu(hfac)3] was prepared simply with only one step. ► Upon excitation, efficient sensitized europium luminescence was indeed achieved.
Keywords: Bimetal; Luminescence; Simpleness; Europium; Sensitizer;

Three types of 1,4-diazabutadiene stabilized low-valent iridium complexes, namely [IrCl(cod)(MesDAB)] (1), [IrCl(coe)(MesDAB)] (2) and [IrCl(MesDAB)2] (3), have been prepared from 1,4-bis(2,4,6-trimethylphenyl)-1,4-diaza-1,3-butadiene (MesDAB) and [IrCl(cod)]2 or [IrCl(coe)2]2, respectively. The complexes have been investigated by NMR spectroscopy and X-ray diffraction experiments. While tetra-coordinated 2 and penta-coordinated 3 maintain their solid state structure in solution, penta-coordinated 1 shows fluxional behavior. The crystal structures determined indicate strong π-backbonding towards the MesDAB ligand in all cases.Three different low-valent iridium complexes containing 1,4-bis(2,4,6-trimethylphenyl)-1,4-diaza-1,3-butadiene (MesDAB) as ligand have been synthesized and characterized. The influence of the metal to ligand ratio as well as the effect of the olefinic co-ligand on the coordination number and the behavior in solution has been studied.Display Omitted► Straightforward strategy for the synthesis of three types of low-valent iridium complexes bearing 1,4-diazadienes. ► Rare example of a low-valent iridium compound containing four neutral nitrogen donor atoms. ► Iridium(I) complexes containing 1,4-diazadiene ligands prefer different structures than diphosphane stabilized compounds.
Keywords: Iridium; Diazabutadiene ligand; Non-innocent ligand; Crystal structure;

Two novel organoantimony(V) complexes [Ph3SbLa]2 (1) and [Ph3SbLb]2 (2) (H2La  = 5-{[(2-carboxyphenyl)methylene]amino}-4-chlorobenzoic acid, and H2Lb  = 5-{[(2-carboxyphenyl)methylene]amino}-2-chlorobenzoic acid) have been synthesized by the reaction of triphenylantimony dichloride and Schiff base ligands with the ratio of 1:1, and characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy. X-ray single-crystal diffraction analyses reveal that two highly symmetrical 24-membered macrocyclic organoantimony derivatives were found unprecedentedly, in which two antimony atoms are bridged by four terminal carboxyl groups of the Schiff base ligands, and antimony atoms exhibit typical five-coordinated trigonal-bipyramid geometry with two carboxyl oxygen atoms occupying the axial positions. In complexes 1 and 2, there exist several types of secondary interactions (C–H…π, C–Cl…π and C-H…Cl), which contribute to the formation of a 1D infinite chain in 1 and a 2D supramolecular network structure in 2 in their crystal structures, respectively.Two novel organoantimony(V) complexes [Ph3SbLa]2 and [Ph3SbLb]2 have been synthesized by the reaction of triphenylantimony dichloride and Schiff base ligands possessing two terminal carboxyl groups, and characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy. Structural analyses reveal that two highly symmetrical 24-membered macrocyclic organoatimony derivatives were obtained unprecedentedly.Display Omitted► Two highly symmetrical 24-membered macrocyclic organoantimony(V). ► Several types of secondary interactions (C-H…π, C-Cl…π and C-H…Cl). ► A 1D infinite chain or 2D supramolecular network structure formed by secondary interaction.
Keywords: Organoantimony(V) complex; Macrocyclic; Schiff base; Crystal structure;

A highly selective chemosensor for Cu2+ and Al3+ in two different ways based on Salicylaldehyde Schiff by Chao Gou; Shao-Hui Qin; Hai-Qiang Wu; Yu Wang; Jing Luo; Xiao-Ya Liu (1622-1625).
A novel, easily available colorimetric and fluorescent double-sensor 1 based on Salicylaldehyde bis-Schiff has been investigated in this work. The sensor exhibits highly selective and sensitive recognition toward Cu2+ in aqueous solution via a naked eye colour change from colourless to yellow and toward Al3+ via a significant fluorescent enhancement in ethanol over a wide range of tested metal ions. This represents the first reported Salicylaldehyde Schiff-based sensor capable of detecting both Cu2+ and Al3+ using two different modes.A novel chemosensor based on Salicylaldehyde bis-Schiff has been investigated. The sensor exhibits colour change from colourless to yellow toward Cu2+ in aqueous solution. It exhibits a significant fluorescent enhancement toward Al3+ in ethanol. It also exhibits aggregation-induced emission enhancement (AIEE) characteristics.Display Omitted► A novel chemosensor based on Salicylaldehyde bis-Schiff has been investigated. ► The sensor exhibits colour change from colourless to yellow toward Cu2+ in aqueous solution. ► It exhibits a significant fluorescent enhancement toward Al3+ in ethanol. ► It also exhibits aggregation-induced emission enhancement (AIEE) characteristics.
Keywords: Chemosensor; Colorimetric; Fluorescence; Cu2+ sensing; Al3+ sensing;

Two new mixed ligand complexes of copper(II) with acetylacetonate (acac) and 2,2′-bipyridine (bpy) belonging to the class of cytotoxic and antineoplastic compounds known as CASIOPEINAS® have been synthesized and characterized on the basis of analytical and spectroscopic data. Molecular structures of the complexes, [Cu(acac)(bpy)Cl][Cu(acac)(bpy)(H2O]Cl.H2O and [Cu(acac)(bpy)Br]H2O, were established by single crystal X-ray study. The Cu(II) ion in both the complexes exhibited square pyramidal geometry with acac and bpy in the equatorial plane and halide/water in the axial position. Interestingly, for the complex with chloride anion, two types of complexes with chloride and water at the axial positions were derived from the same reaction and co-crystallized in the asymmetric unit with strong intermolecular interactions. Microbial property of these two complexes as antibacterial and antifungal agents has been investigated and some of the results are comparable to that of the standard drugs such as E. coli, P. aeruginosa, S. aureus, S. pyogenes, A. niger and C. albicans, used in this study.Two Cu(II) complexes belonging to the class of cytotoxic and antineoplastic compounds known as CASIOPEINAS® have been synthesized and structurally characterized, their microbial activity against standard drugs were studied and the results are encouraging.Display Omitted► Mixed ligand complexes of Cu(II) have been synthesized following a unique synthetic methodology. ► These complexes are known under the trade name CASIOPEINAS®. ► They were characterized crystallographically. ► Two penta coordinated complexes with chloride and water at the axial positions are co-crystallized. ► Antibacterial and antifungal property of these complexes are comparable to some standard drugs.
Keywords: Copper(II) complex; Mixed ligand complex; Casiopeinas®; Crystal structure; Microbial activities;

A new Cu2+-selective self-assembled fluorescent chemosensor based on thiacalix[4]arene by Xiao-jun Hu; Cong-ming Li; Xue-ying Song; Dan Zhang; Yu-shuang Li (1632-1635).
A new ON–OFF fluorescent chemosensor for Cu2+ ions was prepared through self-assembly inside Triton X-100 micelles of p-tert-butylthiacalix[4]arene (TCA) and perylene in water solution. This thiacalix[4]arene-based self-assembled fluorescent chemosensor could realize the direct sensing of Cu2+ ions in aqueous solution. Addition of Cu2+ ions could result in a quenching of the fluorescence emission of perylene inside the micelles, which is ascribed to intramicellar complex-fluorophore electron-transfer or energy-transfer effects induced by the complexation of TCA with the Cu2+ ions. Cu2+ ions can be detected selectively in the presence of other metal ions (Zn2+, Pb2+, Cd2+, Mn2+, Ni2+, Al3+, Na+, K+, Ca2+ and Mg2+) and its concentration in the submicromolar range can be almost linearly determined according to the fluorescence quenching.A new ON–OFF fluorescent chemosensor for Cu2+ ions was prepared through self-assembly inside Triton X-100 micelles of p-tert-butylthiacalix[4]arene (TCA) and perylene in water solution. This thiacalix[4]arene-based self-assembled fluorescent chemosensor could realize the direct selective sensing of Cu2+ ions in aqueous solution.Display Omitted► A new ON–OFF thiacalix[4]arene-based fluorescent chemosensor was prepared. ► This chemosensor was facilely prepared by self-assembly into micelles. ► This chemosensor could realize the direct sensing of Cu2+ ions in water solution. ► Cu2+ ions can be detected selectively in the presence of other metal ions.
Keywords: Thiacalixarene; Fluorescent chemosensor; Self-assembly; Cu2+ ions;

Two new thiocyanato-coordinated manganese(III) complexes with bis-Schiff bases have been unprecedented prepared from N-ethylethane-1,2-diamine and N-(2-hydroxyethyl)ethane-1,2-diamine as the starting materials with equimolar quantities of 4-methoxysalicylaldehyde and 3-ethoxysalicylaldehyde, respectively. It was found that the reaction can process only in the presence of manganese salts and ammonium thiocyanate. The urease inhibitory activity of the complexes was tested.Two new thiocyanato-coordinated manganese(III) complexes with bis-Schiff bases have been unprecedented prepared from mono-Schiff bases. The urease inhibitory activity of the complexes was tested.Display Omitted► Two new manganese(III) complexes with bis-Schiff bases have been unprecedented prepared from mono-Schiff bases. ► The complexes have been characterized by single crystal X-ray diffraction. ► The complexes show urease inhibitory activity. ► The molecular docking study of the complexes with urease was performed.
Keywords: Schiff base; Manganese complex; Synthesis; Crystal structure; Thiocyanate; Urease inhibition;

An inorganic–organic hybrid compound built from polyoxovanadate cluster and Mn (II) complexes by Lei Wang; Yi Li; Yanyan Wang; Zhiqiang Liang; Jihong Yu; Ruren Xu (1640-1643).
A novel inorganic–organic hybrid compound [Mn(teta)][Mn(teta)(H2O)2]2{V18O42(Cl)}·8H2O (1) (teta: triethylenetetramine) has been hydrothermally synthesized and characterized by TGA, IR and XPS analysis. Its structure is determined by single-crystal X-ray diffraction analysis. Compound 1 exhibits a rare 2-D planar square lattice (sql net), which was constructed by the well known {V18O42} cluster as node and two distinct Mn (II) complexes, [Mn(teta)] and [Mn(teta)(H2O)2], as single/double μ 2-bridging linkers. This type sql net with two distinct Mn (II) complexes is the first example found in polyoxovanadates. The magnetic study shows that there exists antiferromagnetic interaction within 1. A novel inorganic–organic hybrid solid [Mn(teta)][Mn(teta)(H2O)2]2{V18O42(Cl)}·8H2O (1) (teta: triethylenetetramine) has been synthesized. It features 2-D planar network constructed by {V18O42(Cl)} cluster and two distinct Mn (II) complexes: [Mn(teta)] and [Mn(teta)(H2O)2] as single/double μ 2-bridging linkers, which is the first example found in polyoxovanadates.Display Omitted ► 1 was constructed by {V18O42(Cl)} cluster and distinct Mn (II) complexes. ► 1 contains two distinct Mn (II) complexes as single/double μ2-bridging linkers. ► The sql net with two distinct Mn (II) complexes is rare in polyoxovanadates.
Keywords: Hydrothermal synthesis; Inorganic–organic hybrid material; Polyoxovanadates; Magnetic properties;

In situ formation of an unprecedented 3D microporous CuCN coordination polymer based on a semirigid tetrahedral linker by You-Long Zhu; Ling-Ling Qu; Jun Zhang; Gen-Wu Ge; Yi-Zhi Li; Hong-Bin Du; Xiao-Zeng You (1644-1647).
An unprecedented three-dimensional (3D) coordination polymer [Cu4(CN)4(tpom)] n (tpom = tetrakis(4-pyridyloxymethylene)methane) (1) was solvothermally prepared and characterized by single-crystal X-ray diffraction, IR, TGA, adsorption and photoluminescent studies. Compound 1 is constructed from a 1D CuCN chain and a tetrahedral ligand tpom, in which the CN ligand was in situ generated by the C―C bond cleavage of acetonitrile molecule under solvothermal conditions. Compound 1 possesses a three-fold interpenetrating framework with ths-z type of rod packing topology. It exhibits relatively high thermal stability up to 330 °C and weak photoluminescent emissions at room temperature. The gas absorption studies revealed that 1 can selectively adsorb 0.8 wt% H2 at 77 K and 1 atmospheric pressure.A triply-interpenetrating microporous coordination polymer was prepared by in situ generation of CN from acetonitrile, which is built on a CuCN chain and tetrahedral tpom ligand, and exhibits weak photoluminescent emissions at RT.Display Omitted► An unprecedented triply-interpenetrating 3D coordination polymer [Cu4(CN)4(tpom)] n with ths-z topology. ► It was formed by in situ generation of CN from acetonitrile. ► It exhibits relatively high thermal stability and weak photoluminescent emissions at RT. ► It selectively adsorbs 0.8 wt% H2 at 77 K and 1 atm.
Keywords: Coordination polymer; Structure; In situ reaction; Adsorption; Photoluminescence;

Size-controlled cubic coordination polymer nanoparticles from chiral dipyridyl Zn-salen by Eui-Hyun Ryu; Jun Ho Lee; Young Sun Lee; Ja-Min Gu; Seong Huh; Suk Joong Lee (1648-1651).
Size-controlled crystalline nanocubic coordination polymer particles from chiral Zn-salen and Co(II) have been obtained. PXRD patterns show that these particles have an identical unit cell regardless of a wide range of size distributions. Furthermore, cubic particles with epitaxial layers have been obtained with a simple manipulation during the synthesis.Crystalline nanocubic coordination polymer particles (CPPs) ranged from 100 nm to 1 μm have been obtained from chiral Zn-salen and Co(II). Their crystallinities are identified by PXRD patterns. Furthermore, cubic particles with epitaxial layers have been obtained with a simple synthetic manipulation.Display Omitted► New class of chiral dipyridyl Zn-salen based nanocubic coordination polymer particles has been synthesized with Co(II). ► The size of nanocubics has been controlled from 100 nm to 1 μm. ► PXRD patterns show that these particles have an identical unit cell regardless of a wide range of size distributions. ► Epitaxial growth of extra layers on cubic particles has been demonstrated. ►Nanocubics are microporous materials which follow a type I isotherm.
Keywords: Coordination polymer particle; Metal-organic frameworks; Cubic; Gas sorption; Epitaxial;

Two novel 3D bimetallic oxide framework with 16-membered wheel clusters based on {Mo5O16} ribbon-like chains by Ming-Xing Yang; Shen Lin; Li-Juan Chen; Xiao-Feng Zhang; Hua Huang (1652-1655).
Two hybrid compounds based on {Mo5O16} ribbon-like chains, [M(3-pt)2(Mo5O16)]·H2O (M = Co, Mn) (1 and 2) {3-pt = 5-(3-pyridyl)-tetrazole}, have been hydrothermally synthesized and characterized by single crystal X-ray diffraction. Three-dimensional Mo/O/MII/tetrazole frameworks of the title compounds are constructed from 1D infinite ribbon-like [Mo5O16]2− chains covalently linked through [M(3-ptz)]2+ fragments via O―M and N―Mo coordinate bonds. It is noteworthy that the isostructural compounds contain an unprecedented 3D bimetallic oxide network with 16-membered wheel clusters in which two parallel interdigitated stacks of 3-pt ligands are trapped. Remarkably, the title complexes represent the first two examples of the solid materials containing {Mo5O16} ribbon-like chains.Two 3D Mo/O/MII/tetrazole framework compounds are constructed from 1D infinite ribbon-like [Mo5O16]2− chains covalently linked through [M(3-ptz)]2+ fragments via O―M and N―Mo coordinate bonds. The title isostructural compounds contain an unprecedented 3D bimetallic oxide network with 16-membered wheel clusters in which two parallel interdigitated stacks of 3-pt ligands are trapped and represent the first two examples of the solid materials containing {Mo5O16} ribbon-like chains.Display Omitted► Two compounds show very interesting 3D bimetallic oxide networks. ► The 3D frameworks contain 16-membered wheel clusters. ► They are the first two examples of the solid materials containing {Mo5O16} chains.
Keywords: Inorganic–organic hybrid materials; Polyoxomolybdate; Bimetallic oxides;

Fluoranthene-based pyridine as fluorescent chemosensor for Fe3+ by Zhan-Xian Li; Li-Feng Zhang; Wan-Ying Zhao; Xiao-Ya Li; Yong-Kai Guo; Ming-Ming Yu; Jin-Xia Liu (1656-1658).
A fluoranthene based fluorescent chemosensor 2-(7,10-diphenyl-fluoranthen-8-yl)-pyridine (B) which shows excellent selectivity towards Fe3+ is described. Upon addition of FeCl3 into the ethanol solution of B, it exhibits a great decrease of emission intensity against environmental and biological samples. Further experiments demonstrate that Fe(NO3)3 has the similar influence as FeCl3 on the emission spectra of B while Fe2(SO4)3 has no influence on that of B.Fluorescent chemosensor B shows excellent selectivity towards Fe3+, no fluorescence change was found even when the amount of these alkali and alkaline earth metal ions was at a high concentration of 6 mM.Display Omitted► A fluoranthene-based fluorescent Fe3+-chemosensor B is synthesized. ► B can detect Fe3+ against competing metal ions through ON–OFF fluorescent behavior. ► Either Fe(NO3)3 or FeCl3 can quench the emission of B while Fe2(SO4)3 cannot.
Keywords: Fluoranthene; Fluorescent chemosensor; Fe3+ sensor;

Water-soluble Pt3S2 cluster with phosphine ligands by Maxim N. Sokolov; Alexander V. Anyushin; Alexander V. Virovets; Irina V. Mirzaeva; Nina F. Zakharchuk; Vladimir P. Fedin (1659-1660).
Reaction of [Pt(P(CH2OH)3)2Cl2] with H2S in methanol produces new water-soluble trinuclear complex [Pt33-S)2(P(CH2OH)3)6]Cl2 (1). It was characterized by IR-spectroscopy, 31P NMR, X-ray structure analysis, mass-spectra and cyclic voltammetry.Reaction of [Pt(P(CH2OH)3)3Cl2] with H2S in methanol produces a new water-soluble trinuclear complex [Pt33-S)2(P(CH2OH)3)6]Cl2. It was characterized by IR-spectroscopy, 31P NMR, X-ray structure analysis, mass-spectra and cyclic voltammetry.Display Omitted▶ [Pt(P(CH2OH)3)2Cl2] with H2S gives water-soluble [Pt33-S)2(P(CH2OH)3)6]Cl2. ▶ The only reaction product. ▶ Characterized by IR, 31P NMR, X-ray analysis, ESI-MS and CVA. ▶ The structure preserved in solution. ▶ Potential applications in environmentally friendly catalytic processes.
Keywords: Platinum complexes; Sulfide clusters; Water-soluble phosphines; Crystal structures;

New high-spin bis-o-semiquinonato cobalt(II) complexes with neutral donor ligands by Natalia A. Pavlova; Andrey I. Poddel'sky; Artem S. Bogomyakov; Georgy K. Fukin; Vladimir K. Cherkasov; Gleb A. Abakumov (1661-1664).
Two novel bis-o-semiquinonato cobalt complexes Co(3,6-SQ)2L (1, L1  = 2,6-dimethyl-N-(pyridin-2-ylmethylene)benzenamine; 2, L2  = 2,6-dimethyl-N-(thiophen-2-ylmethylene)benzenamine; 3,6-SQ is 3,6-di-tert-butyl-o-benzosemiquinonato radical-anion) were synthesized. According to X-ray analysis, complex 2 adopts square pyramidal geometry with N-coordinated neutral ligand L2 in the apical site. According to magnetic susceptibility measurements and spectroscopic studies, both complexes contain high-spin cobalt(II) (d7, S = 3/2) and two radical-anionic o-semiquinonato ligands. There is antiferromagnetic metal–ligand and ligand–ligand coupling in 1, while complex 2 demonstrates weak antiferromagnetic ligand–ligand coupling at low temperature and ferromagnetic metal–ligand exchange at 150–300 K.Two new high-spin bis-o-semiqiunonato cobalt complexes containing nitrogen donor ligands were prepared. Complex with thiophene-containing ligand is pentacoordinated. The magnetic properties of both complexes have been investigated: Co(II) is high spin (S = 3/2) and the antiferromagnetic exchange interaction between paramagnetic ligands takes place; complexes demonstrate different metal–ligand magnetic exchange.Display Omitted► Two new bis-o-semiquinonato cobalt complexes of Co(3,6-SQ)2L were prepared. ► Co(3,6-SQ)2L (ArN = CH-thiophene) is the first pentacoordinate cobalt(II) bis-semiquinolate. ► Complexes contain high-spin cobalt(II) and two radical-anionic o-semiquinones. ► Different magnetic behaviorswere found for complexes with ArN = CH-thiophene/pyridine.
Keywords: Cobalt; o-semiquinone; N-donor ligand; Magnetochemistry; X-ray analysis;

Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four Ag―P bonds. The in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry.Complex [Ag2(dppatc)2](NO3)2·2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1) was generated from the in situ reaction of AgNO3 with N,N,N',N'-tetra(diphenylphosphanylmethyl)ethylenediamine and aminothiocarbamide. The dppatc ligand could be readily formed by reaction of diphenylphosphine with formaldehyde and aminothiocarbamide while reaction of AgNO3 with dppatc produced 1 in high yields.Display Omitted► Reaction of AgNO3 with dppeda and aminothiocarbamide gave complex 1 in a low yield. ► The dppatc ligand could be readily generated by the reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. ► Reactions of AgNO3 with dppatc produced 1 in a relatively high yield.
Keywords: Silver(I); N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide; Crystal structure; Aminothiocarbamide; In situ formation;

A novel (3,4,8)-connected 3D topology framework based on [Gd2(bpdc)3(H2O)3] second building units by Rui-ping Liu; Jun Li; Gui-ping Yao; Yun Luo; Dario Braga; Feng-Xing Zhang (1669-1672).
A new 3D coordination polymer {[Gd2(bpdc)3(H2O)3]·H2O}n (1) has been isolated from the reaction of 2,2′-bipyridine-4,4′-dicarboxylic acid (H2bpdc) and Gd(III) salts under hydrothermal conditions. Single-crystal X-ray diffraction study shows that compound 1 is constructed from Gd2-based second building units (SBUs) [Gd2(bpdc)3(H2O)3] and displays a 3D (3,4,8)-connected net with (42·6)(32·42·52)(32·45·54·611·76) topology. A thermogravimetric analysis of 1 shows a high thermal stability. The magnetic behavior of 1 reveals a weak antiferromagnetic interaction between Gd(III) ions.A new (3,4,8)-connected 3D coordination polymer {[Gd2(bpdc)3(H2O)3]·H2O}n based on 2,2′-bipyridine-4,4′-dicarboxylic acid (H2bpdc) and Gd(III) salts was constructed. It displays high thermal stability and a weak antiferromagnetic interaction between Gd(III) ions.Display Omitted► A new 3D Gd(III) coordination polymer has been isolated under hydrothermal condition. ► Compound 1 shows a new (3,4,8)-connected 3D coordination network. ► The (3,4,8)-connected topology was first reported in the lanthanide complex here. ► The magnetic behavior of compound 1 revealed the weak antiferromagnetic interactions between two Gd ions.
Keywords: Metal organic framework; Crystal structure; Coordination polymer; Magnetic property;

Syntheses, structures and catalytic activities of ruthenium (II) carbonyl iodide complexes with CNC-pincer bis (carbene) ligand by Xiao-Wei Li; Fei Chen; Wei-Feng Xu; Yi-Zhi Li; Xue-Tai Chen; Zi-Ling Xue (1673-1676).
Two new pincer bis (carbene) ligands and corresponding ruthenium (II) carbonyl iodide complexes have been synthesized and characterized. The structures of complexes 3 and 4 have been determined by X-ray crystallography. Complexes 3 and 4 have been proved to be efficient catalysts in the transfer hydrogenation of acetophenone.Two Ru (II) carbonyl iodide complexes with pincer bis (carbene) ligands have been synthesized and demonstrated to be effective in the transfer hydrogenation of acetophenone by 2-propanol.Display Omitted► Two bis(carbene) ligands and corresponding ruthenium(II) complexes have been synthesized and characterized. ► The structures of two new complexes have been determined by X-ray crystallography study. ► Two new complexes have been proved to be efficient catalysts in the transfer hydrogenation of acetophenone.
Keywords: Ruthenium; N-heterocyclic carbene; Catalysis; Transfer hydrogenation;

Layered zinc 4-phosphonoisophthalates pillared by flexible bis(imidazole) Co-ligands by Hao-Jun Jin; Peng-Fei Wang; Cheng Yao; Li-Min Zheng (1677-1680).
This paper reports two zinc phosphonates based on 4-phosphonoisophthalic acid (4-piH4) and bis(imidazole) co-ligands, namely, [Zn2(4-pi)(1,2-bix)] (1) and [Zn2(4-pi)(1,3-bix)] (2) (1,2-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, 1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene). Both show layer structures in which the inorganic tetranuclear cores of Zn4P2O6 are connected by 4-pi4−ligands. The 1,2-bix or 1,3-bix ligand binds to the Zn atoms within the tetranuclear unit or between the neighboring tetranuclear units in a cis-coordination mode, and fill in the interlayer spaces in both cases. The luminescent properties are investigated.Mixed ligated zinc phosphonates [Zn2(4-pi)(1,2-bix)] (1) and [Zn2(4-pi)(1,3-bix)] (2) based on 4-phosphonoisophthalic acid (4-piH4) and 1,2-,1,3-bis(imidazol-1-ylmethyl)benzene show layer structures in which the inorganic tetranuclear cores of Zn4P2O6 are connected by 4-pi4−ligands. The luminescent properties are investigated.Display Omitted► Mixed ligated zinc phosphonates with layer structures. ► Zinc 4-phosphonoisophthalate with bis(imidazole) co-ligands. ► Hybrid metal phosphonates containing inorganic tetranuclear cores.
Keywords: Zinc; 4-Phosphonoisophthalic acid; Bis(imidazol-1-ylmethyl)benzene; Crystal structure;

Structural characterization of three organically modified Cd(II) compounds by Juan Jin; Ming-Jun Jia; Yu-Chang Wang; Jie-Hui Yu; Qing-Feng Yang; Ji-Qing Xu (1681-1684).
Based on a strategy of introducing the inorganic SCN group into CdX2-organoamine system, three organically modified Cd(II) compounds as 1-D [H2dmpip][CdCl3(SCN)] (dmpip =  N,-Dimethylpiperazine) 1, 2-D [Cd(SCN)2(dach)] (dach = 1,4-Diazacycloheptane) 2 and mononuclear [CdI3(Hdach)] 3 were obtained in H2O/C2H5OH solutions under ambient conditions. X-ray single-crystal diffraction analysis revealed that compound 1 is diprotonated dmpip-templated chained cadmium-chloro thiocyanate, compound 2 is the first example of dach-extended layered cadmium-thiocyanato coordination polymer, and compound 3 is monoprotonated dach-coordinated mononuclear cadmium iodide. The photoluminescence analysis indicates that the title three compounds are the potential fluorescence materials.By introducing inorganic anionic group SCN into CdX2-organoamine system in H2O/C2H5OH solutions, three new organically modified Cd(II) compounds [H2dmpip][CdCl3(SCN)] 1, [Cd(SCN)2(dach)] 2 and [CdI3(Hdach)] 3 (dmpip =  N,N'-Dimethylpiperazine, dach = 1,4-Diazacycloheptane) were obtained by room-temperature self-assemblies.Display Omitted► This article is based on a simple strategy of incorporating inorganic SCN– group into CdX2-organoamine system. ► Three new organically modified Cd(II) complexes were synthesized under ambient conditions. ► The structural characterization of the first example of dach-extended coordination polymer was reported. ► The reason that dach could act as the different roles in the complex was analyzed.
Keywords: Halocadmate; Coordination polymer; Self-assembly; Organic amine; Fluorescence;

Mass-spectroscopy of polynuclear palladium carboxylate complexes as a key to new structures. Synthesis and X-Ray structure of Pd12(μ-CO)8(μ-NO2)8(μ- i PrCO2)8 by Oleg N. Shishilov; Andrei V. Churakov; Lyudmila G. Kuz'mina; Nailya S. Akhmadullina; Inessa A. Efimenko (1685-1689).
Palladium NOx-containing polynuclear carboxylate complexes Pd4(μ-CO)2(μ-NO)(μ- i PrCO2)5 and Pd8(μ-CO)4(μ-NO2)4(μ- i PrCO2)8 were studied with MALDI-TOF mass-spectroscopic technique. The results confirm previous suggestion about Pd4 metal chains as building blocks for big palladium carbonyl carboxylate clusters. Also a new Pd3 bent metal chain observed in mass-spectra was demonstrated to serve a building block as well. Using the data the biggest palladium carboxylate cluster Pd12(μ-CO)8(μ-NO2)8(μ- i PrCO2)8 was synthesized and characterized by X-Ray analysis. Thus it was shown that mass-spectroscopic data for palladium carboxylates can be used for prediction of new structures of palladium clusters.Palladium NOx-containing polynuclear carboxylate complexes Pd4(μ-CO)(μ-NO)(μ- i PrCO2)5 and Pd8(μ-CO)4(μ-NO2)4(μ- i PrCO2)8 were studied with MALDI-TOF mass-spectroscopic technique. A new Pd3 bent metal chain observed in mass-spectra was demonstrated to serve a building block as well. Using the data the biggest palladium carboxylate cluster Pd12(μ-CO)8(μ-NO2)8(μ- i PrCO2)8 was synthesized and characterized by X-Ray analysis.Display Omitted► MALDI-TOF MS-study of Pd4(CO)2(NO)(RCO2)5 and Pd8(CO)4(NO2)4(RCO2)8 clusters was carried out. ► New high-stable fragment of palladium carboxylate clusters – bent Pd3-chain – was observed. ► New approach to synthesis of high-nuclear palladium carboxylate cluster was proposed and tested. ► The biggest palladium carboxylate cluster Pd12(CO)8(NO2)8(RCO2)8 was characterized by X-Ray diffraction analysis.
Keywords: Palladium; Carbonyl; Carboxylate; MALDI TOF mass-spectroscopy; X-Ray diffraction analysis;

One 3d–4f heterometallic polymer, namely, {[Eu2Cu(PDC)2(SO4)2(H2O)6]·2H2O}n (H2PDC = pyridine-3,5-dicarboxylic acid), has been successfully synthesized under hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis reveals that the polymer features an unusual three-dimensional network structure in which infinite lanthanide-carboxylate chains are linked by [Cu(SO4)2]2− metalloligands to form a mixed-metal coordination network. Furthermore, luminescent property of the hybrid material has also been investigated at room temperature.One new 3d-4f heterometallic polymer based on organic pyridinedicarboxylic acid and inorganic lanthanide sulfate skeletons has been successfully synthesized and structurally characterized. The polymer features an unusual three-dimensional network structure in which infinite lanthanide-carboxylate chains are linked by [Cu(SO4)2]2− metalloligands to form a mixed-metal coordination network.Display Omitted► One new 3d-4f polymer based on lanthanide sulfate has been synthesized. ► The compound structure was identified by single-crystal X-ray diffraction analysis. ► Luminescent property of the compound was investigated at room temperature.
Keywords: Pyridine-3,5-dicarboxylate; Hydrothermal synthesis; 3d–4f hybrid polymer; Luminescent property;