Inorganic Chemistry Communications (v.58, #C)

Content List (iii-x).

Two coordination polymers, formulated as {[Cd(1,4-BDC)(ppene)]·CH3CN} n (1) and [Cd(H2O)(1,2,4-HBTC)(ppene)0.5] n (2) have been synthesized through the solvothermal reactions between Cd(NO3)2·4H2O and 4-pyr-poly-2-ene (ppene) in the presence of 1,4-benzenedicarboxylic acid (1,4-H2BDC) or its derivative 1,2,4-benzenetricarboxylic acid (1,2,4-H3BTC). These two compounds were structurally characterized by infrared spectroscopy, elemental analysis, single crystal X-ray diffraction and powder X-ray diffraction. Compound 1 exhibits a three-dimensional two-fold interpenetrating 41263 -pcu network. The coordination network of 2 shows a three-dimensional (4,5)-connected framework with rare (4462)(4466) tcs topology. Owing to the linkage of hydrogen bonding interactions between protonated carboxylic groups, 2 further displays a three-dimensional (5,5)-connected supramolecular network with an unprecedented Schläfli symbol (4862)(4664). Thermal stability and photoluminescence properties of 1 and 2 were also investigated.Two different coordination networks {[Cd(1,4-BDC)(ppene)]·CH3CN} n (1) and [Cd(H2O)(1,2,4-HBTC)(ppene)0.5] n (2) have been prepared by the assemblies of Cd(NO3)2, ppene and 1,4-H2BDC or 1,2,4-H3BTC, respectively. Their thermal and photoluminescence properties were also investigated.Display Omitted
Keywords: Coordination polymers; Carboxylic group; Syntheses; Topological analyses; Photoluminescence properties;

Two new anion-induced chiral complexes have been synthesized via a chiral bis-chelating organic bridging ligand and changing the counteranions, in which 1 displays a one-dimensional linear chain, while 2 is a binuclear structure. Circular dichroism (CD) spectra confirm that they are of structural chirality in the bulk samples. The luminescence properties indicate that they may have potential applications as optical materials. The present study demonstrates that the anion is a crucial factor for the construction of coordination polymers.Two anion-induced chiral Ag(I) complexes have been synthesized by using a chiral bis-chelating organic bridging ligand and changing the counteranions. Their CD spectra and luminescence properties have been discussed.Display Omitted
Keywords: Anion-induced; Chiral Ag(I) complex; Circular dichroism spectra; Luminescence;

A pair of novel helical Zn(II) enantiomers constructed from l - and d -threonine Schiff bases: Synthesis, crystal structures and properties by Jun-Ni Mao; Lin Du; Zong-Ze Li; Quan Wang; Kai-Min Wang; Jing-Song Zhao; Jie Zhou; Tong Yan; Shao-Hua Li; Qi-Hua Zhao (9-13).
Two novel homochiral helical Zn(II) coordination polymers, {[Zn2(nap- l -thr)2(H2O)2]·H2O}n (1) and {[Zn2(nap- d -thr)2(H2O)2]·H2O}n (2) (H2nap- l -thr =  N-(2-hydroxy-1-naphthylmethylidene)- l -threonine, H2nap- d -thr =  N-(2-hydroxy-1-naphthylmethylidene)- d -threonine) have been successfully synthesized and characterized by elemental analysis, IR, UV–visible and single-crystal X-ray diffraction. It is interesting to note that both complexes are a pair of enantiomers: 1 exhibits 1D right-handed helical chain of [Zn-COO] and 2 is 1D left-handed helical chain of [Zn-COO]. There are various hydrogen bonds between the adjacent helical chains which result in a 2D homochiral supramolecular layer structure. Notably, under similar synthetic procedure by using the NO3 , CH3COO, Cl salts of Zn2 + ion as a starting reagent, and identical compounds were obtained. In addition, the chiral nature of complexes 1 and 2 are confirmed by the results of circular dichroism (CD) spectra measurements. Thermal stability and luminescence properties were also investigated.A pair of enantiomers of Zn(II) coordination polymers have been constructed from l - and d -threonine Schiff bases, and two Zn(II) complexes 1 and 2 exhibit interesting 1D right- and left-handed helical chains, respectively. Both complexes were characterized by X-ray crystallography, PXRD, TGA, CD measurements and luminescence properties.Display Omitted
Keywords: Enantiomers; Schiff base; Threonine; Homochiral helical chain; Luminescence properties;

Hydrothermal reaction of Cu(NO3)2·3H2O with BIBP and H2hfipbb at 105 °C yielded a novel 3D Cu(II) coordination polymer, {[Cu2(BIBP)0.5(hfipbb)2(CH3CN)]·5H2O} n (1) [BIBP = 5,5′-bis(1H-imidazol-1-yl)-2,2′-bithiophene, H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)]. Compound 1 displays a 3D 2-fold interpenetrating framework with {44.66} sqp topology, containing interesting ⋯LRLR⋯ double helical chains. The compound 1 was characterized by IR spectra, elemental analysis, thermal analysis and single crystal X-ray diffraction. In addition, solid-state UV–vis spectra experiment shows that compound 1 exhibits semiconductive property with a band gap of 2.46 eV.A new 2-fold interpenetrated 3D Cu(II) coordination polymer {[Cu2(BIBP)0.5(hfipbb)2(CH3CN)]·5H2O} n with thiophene-containing ligand has been synthesized. The compound exhibits {44.66} sqp topology containing interesting ⋯LRLR⋯ double helical chains and shows semiconductive property.Display Omitted
Keywords: Cu(II) coordination polymer; Semiconductive property;

The first carbamoyl–carboxylate complex of transition metals: Synthesis and structure of {(OC4H8NH)[OC4H8NC(=O)]Pd}2(μ-CMe3CO2)2 by Oleg N. Shishilov; Ivan M. Kumanyaev; Nailya S. Akhmadullina; Andrei V. Churakov; Irina A. Garbuzova; Vitaly R. Flid (16-19).
Reactions of palladium(I) carbonyl carboxylate complexes [Pd(μ-CO)(μ-RCO2)] n with secondary amines on the example of morpholine were studied. It was found that intramolecular carbonylation of amine in coordination sphere of polynuclear palladium species proceeds and binuclear palladium carbamoyl complex {(OC4H8NH)[OC4H8NC(=O)]Pd}2(μ-RCO2)2 forms as a result. This is the first structurally characterized carbamoyl–carboxylate complex of transition metals. Also it was shown that morpholine itself and carboxylate-anions act as proton acceptors in the reaction of carbonylation of morpholine by coordinated CO.Reactions of palladium(I) carbonyl carboxylate complexes [Pd(μ-CO)(μ-RCO2)] n with secondary amines on the example of morpholine were studied. It was found that intramolecular carbonylation of amine in coordination sphere of polynuclear palladium species proceeds and binuclear palladium carbamoyl complexes {(OC4H8NH)[OC4H8NC(=O)]Pd}2(μ-RCO2)2 forms as a result.Display Omitted
Keywords: Palladium; Carboxylate; Amine; Carbonylation; Carbamoyl complex;

Se4CuX, Te4CuX and Cu2Se7X2 (X = GaCl4) — Coordination compounds of neutral infinite chalcogen chains by Andreas Eich; Yaser NejatyJahromy; Olav Schiemann; Johannes Beck (20-23).
The reactions of selenium and tellurium in molten GaCl3 with SbCl3 and copper(II) or copper(I) chloride yielded CuSe4[GaCl4] (1), CuTe4[GaCl4] (2), and Cu2Se7[GaCl4]2 (3). EPR measurements show no resonances, implying the presence of monovalent Cu ions. The structures consist of discrete infinite neutral chalcogen chains of helical shape. Cu(I) ions are coordinated to the Se and Te chains via three chalcogen atoms for the isotypic 1 and 2, and via two Se atoms for 3. The coordination tetrahedron for Cu is completed by coordination of Cl atoms of neighboring [GaCl4] anions.
Keywords: Tetrachlorido gallate; Chalcogen chains; Copper(I);

Synthesis and recognition properties for copper ions and cyanide anions of two coumarin hydrazide compounds by Lin Ma; Yongxiao Xu; Kangnan Wang; Chuanjian Zhou; Duxia Cao; Yanyan Shan; Qianqian Wu (24-26).
Two coumarin hydrazide compounds were synthesized by 7-N,N-diethylaminecoumarin-3-formyl chloride and 2-pyridinecarboxylic acid hydrazide or benzoylhydrazine. The compounds are found to be able to recognize copper ions and cyanide anions accompanied by obvious UV–vis absorption change and fluorescence turn-off response. Mechanism studies suggested that complexation between compounds and copper forms and cyanide may be bonded to 4-position of coumarin.Two coumarin hydrazide compounds as chemosensors for copper and cyanide were synthesized and can recognize copper ions and cyanide anions with obvious absorption change and fluorescence turn-off response.Display Omitted
Keywords: Copper; Coumarin hydrazide; Cyanide; Fluorescence change;

Syntheses, structures and properties of cobalt and manganese complexes based on pyridine-2,3,5,6-tetracarboxylic acid by Hong-Ling Gao; Yan-Xia Bi; Fang-Fang Li; Chi Wai Cheung; Wen-Min Wang; Hai-Yun Shen; Jian-Zhong Cui (27-30).
Two new complexes based on pyridine-2,3,5,6-tetracarboxylic acid(H4pdtc) as ligand, {[Co2(pdtc)(H2O)4] · H2O}n (1) and {Mn2(pdtc)(H2O)4}n (2), have been obtained by hydrothermal syntheses and characterized by IR, elemental analysis, X-ray diffraction single crystal structure analysis, PXRD, thermal gravimetric analysis, and magnetic measurements. Complex 1 is 3D coordination polymer and complex 2 belongs to 2D grid structure by covalent bonds. In 1 and 2, the metal ions show antiferromagnetic interactions.Two complexes based on pyridine-2,3,5,6-tetracarboxylic acid are prepared. Their structures and properties have been investigated. The pyridine-2,3,5,6-tetracarboxylic acid contains rich coordination sites, which can adopt a variety of coordination modes in the structure. Furthermore, the most interesting thing is that, the oxygen atoms and nitrogen atom in the same pdtc4 − anion are all coordinated with Mn(II) ions, which is reported the first time.Display Omitted
Keywords: Pyridine polycarboxylic acid; Hydrothermal synthesis; 3D coordination polymer; Magnetic property;

3D supramolecular open-framework constructed by inorganic [B5O6(OH)4] and organic [CH3COO] anions by Xia Li; Guanghua Li; Ling Wang; Mingyu Shang; Dan Zhang; Yunling Liu; Hongming Yuan; Shouhua Feng (31-34).
A borate compound [Ni(en)3][B5O6(OH)4][CH3COO] (1) has been synthesized under mild hydrothermal conditions. The newly synthesized compound was characterized by single-crystal X-ray diffraction, elemental analysis and thermogravimetry. The three-dimensional (3D) supramolecular open-framework of compound 1 is constructed by inorganic [B5O6(OH)4] building units and organic [CH3COO] anions through hydrogen bonds, and the charge-balancing [Ni(en)3]2 + cations are located in 3D channels. It is very interesting that there exist two helical chains formed by [B5O6(OH)4] building units and organic [CH3COO] anions through hydrogen bonds in compound 1 along different axes. Magnetic measurement indicates that compound 1 exhibits paramagnetic behavior down to 4 K.The inorganic [B5O6(OH)4] and organic [CH3COO] anions co-constructed 3D supramolecular open-framework which exist two helical chains through hydrogen bonds in the compound along different axes.Display Omitted
Keywords: Borate; Acetate; Hydrothermal synthesis; Supramolecular open-framework;

Bis(1,3,5-triazapentadienate)zinc complexes [N(Ph)C(R)NC(R)N(SiMe3)]2Zn (R = NMe2, 1; 1-piperidino, 2) and (1,3,5-triazapentadienate)aluminum dichloride [N(Ph)C(NMe2)NC(NMe2)N(SiMe3)]AlCl2·C9H18N6 (3) were synthesized and structurally characterized by X-ray crystallography and spectroscopic techniques. The X-ray structures of 13 showed that they crystallize in the triclinic system and prefer coordination to the zinc and aluminum centers via the terminal N atoms of the NCNCN ligand backbone, affording tetrahedral geometry. The catalytic properties of 1 and 2 were evaluated.Three 1,3,5-triazapentadienate–zinc and 1,3,5-triazapentadienate–aluminum complexes are reported. Their structural features are discussed and their catalytic properties have been evaluated.Display Omitted
Keywords: Triazapentadienyl; Zn and Al complexes; Crystal structures; Catalytic property;

BiPO4 film on ITO substrates for photoelectrocatalytic degradation by Teng Zeng; Xiang Yu; Kai-Hang Ye; Zhiguang Qiu; Yi Zhu; Yuanming Zhang (39-42).
BiPO4 film was fabricated on indium-tin oxide glass substrate via dip-coating method for photoelectrocatalytic (PEC) activity. BiPO4 film has performed a superior PEC degradation ability with synergetic effect of electro-oxidation and photocatalysis. The degradation rate of Methyl Blue (MB) increased greatly as bias potential increased and the highest activity was achieved at the bias potential of 3.0 V (vs. SCE in 0.1 mol/L Na2SO4, pH = 7). The PEC activity of BiPO4 film is 5 times and 15 times higher than that of photocatalytic degradation and electrochemical oxidation, respectively. The acid condition plays an important role in achieving effective photoelectrocatalysis. The PEC degradation rate was also affected by the adsorption and the oxidation reaction of the ions of electrolytes. This BiPO4 film could open up new opportunities to develop high-performance photoanode for PEC degradation.The BiPO4 film loaded on the ITO substrate was used as electrode during the reaction. The applied bias effectively enhanced the separation of photo-induced electron-hole.Display Omitted
Keywords: BiPO4; Film; Photoelectrocatalysis; Organic degrade;

Two novel pillar-layered Mn(II) coordination networks based on aromatic carboxylic acids with aminodiacetate functionality by Jie Ma; Fei-Long Jiang; Lian Chen; Ming-Yan Wu; Kang Zhou; Wen-Tao Yi; Jie Xiong; Mao-Chun Hong (43-47).
By utilizing 2-aminodiacetic terephthalic acid (H4adtp) and N-(4-carboxyphenyl)iminodiacetic acid (H34-cpida), two coordination polymers formulated as [Mn(H2adtp)(H2O)]n (1) and [Mn3(4-cpida)2(H2O)2]n (2) have been synthesized under solvothermal conditions without any secondary linker. 1 is a three-dimensional (3D) supramolecular pillar-layered structure, where double hydrogen bonding two H2adtp ligands act as one pillar. 2 is a genuine 3D pillar-layered framework with phenyl moiety as strut. Aminodiacetate functionalities in 1 and 2 demonstrate unprecedented ability in connecting the metal ions into 2D layers. Magnetism studies indicate that two complexes both exhibit dominant antiferromagnetic behaviors. In addition, the fitting of magnetic susceptibility (χM) of 1 is performed based on the model of the alternating –J 1 J 2– coupling chain and considering molecular-field approximation.By utilizing 2-aminodiacetic terephthalic acid (H4adtp) and N-(4-carboxyphenyl)iminodiacetic acid (H34-cpida), two pillar-layered coordination polymers formulated as [Mn(H2adtp)(H2O)]n (1) and [Mn3(4-cpida)2(H2O)2]n (2) have been synthesized under solvothermal conditions without any secondary linker, where double hydrogen bonding two H2adtp ligands act as one pillar in 1. Aminodiacetate functionalities in 1 and 2 demonstrate unprecedented ability in connecting the metal ions into 2D layers. Magnetism studies indicate that two complexes both exhibit dominant antiferromagnetic behaviors.Display Omitted
Keywords: 2-Aminodiacetic terephthalic acid; N-(4-carboxyphenyl)iminodiacetic acid; Pillar-layered; Antiferromagnetic; –J 1 J 2–;

Crystal structure and catalytic studies of heterodinuclear complex [CuZn(μ-OAc)(μ-OH)(μ-OH2)(bpy)2](ClO4)2 by Sankey Shangpung; A. Kumar; M. Asthana; A.K. Dey; Sunshine D. Kurbah; D. Basumatary; R.A. Lal (48-52).
The heterodinuclear copper–zinc complex [CuZn(μ-OAc)(μ-OH)(μ-OH2)(bpy)2](ClO4)2 has been synthesized from solid state reaction and its crystal structure was established. The heterobimetallic complex is quite efficient catalyst for hydrogen peroxide mediated oxidation of alcohols into corresponding carbonyl compounds.The newly synthesized heterobimetallic complex [CuZn(μ-OAc)(μ-OH)(μ-OH2)(bpy)2](ClO4)2, characterized by various physico-chemical, spectroscopic techniques and finally by X-ray crystallography, is quite efficient catalyst for hydrogen peroxide mediated oxidation of alcohols into a corresponding carbonyl compounds.Display OmittedScheme 1: Oxidation of alcohols.

One novel porphyrin 5,10,15,20-tetra(4-(4-acetateethyl)phenoxy)phenylporphyrin (H2Pp), and its two corresponding zinc(II) and copper(II) porphyrins (ZnPp, CuPp) is synthesized and characterized by spectroscopic techniques. The single crystal structures of [ZnPp(DMF)]·DMF (1) and [CuPp(DMF)] (2) are also obtained and analyzed. Complex 1 crystallizes in monoclinic system compared to the triclinic system of complex 2, which may due to the influence of solvent DMF molecule in 1. The metal centers have similar coordination environments in the two structures, which are all five-coordinated pyramid geometry with four nitrogen atoms of porphyrin ring from equator and an axial oxygen atom of DMF molecule. 1 and 2 display 3D supramolecular structures constructed by π⋯π interactions of porphyrin rings and C–H⋯O hydrogen bonds. The catalytic activities of 1 and 2 to the ethylbenzene oxidation are examined. The results indicate that both of them exhibit highly selectivity to acetophenone (> 99%) with the conversion of 23% (1) and 76% (2) respectively.Two novel supramolecular structures of zinc(II), copper(II) porphyrins were analyzed, and copper(II) porphyrin showed high catalytic activities to the ethylbenzene oxidation.Display Omitted
Keywords: Porphyrin; Zinc(II) porphyrin; Copper(II) porphyrin; Crystal structure; Catalytic oxidation;

Structures and antitumor activities of planar chiral cyclopalladated ferrocene derivatives by Dongyuan Ning; Yuan Cao; Yuanyuan Zhang; Linghao Xia; Gang Zhao (57-59).
Bis(μ-acetato)-bridged planar chiral cyclopalladated products have been obtained by asymmetric cyclopalladation of the corresponding chiral ferrocenylimines with palladium(II) acetate and sodium acetate in methanol at room temperature. Two diastereomers were isolated in enantiomerically pure form and their absolute configurations have been determined by single-crystal X-ray analysis. It was found that enantiomerically pure cyclopalladated ferrocene displayed the excellent inhibition to two human breast carcinoma cell lines, MDA-MB-231 and MDA-MB-468 and could have good application prospect in pharmaceutical use.Anti-cancer active planar chiral cyclopalladated product was prepared and isolated in enantiomerically pure form.Display Omitted
Keywords: Cyclopalladated compound; Planar chirality; Crystal structure; Antitumor activities;

A new 3D Ni(II)-MOF {[Ni3(ImhedpH)2(4,4′-bipy)]·4,4′-bipy·4H2O} n (1), based on 2-(1-imidazole)-1-hydroxyl-1,1′-ethylidenediphosphonate and 4,4′-bipyridyl, is presented, which possesses a (4,4)-connected frl-(42·64)4(64·82) network and shows ferrimagnetism and field-induced magnetic transition from ferrimagnetism to fully polarized state.A new 3D Ni(II)-MOF, {[Ni3(ImhedpH)2(bpy)]·bpy·4H2O} n (1) constructed from polymeric chains is presented, which possesses a (4,4)-connected frl-(42·64)4(64·82) network.Display Omitted
Keywords: NiII-MOFs 2-(1-imidazole)-1-hydroxyl-1,1′-ethylidenediphosphonic acid; 4,4′-Bipyridyl; Magnetic property;

Hexafluoridophosphate partial hydrolysis leading to the one-dimensional coordination polymer [{Cu(xantphos)(μ-PO2F2)} n ] by Sarah Keller; Fabian Brunner; Alessandro Prescimone; Edwin C. Constable; Catherine E. Housecroft (64-66).
The one-dimensional coordination polymer [{Cu(xantphos)(μ-PO2F2)} n ] (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) is reported, the first extended structure in which copper(I) centres are linked by μ-PO2F2 units.The first one-dimensional coordination polymer in which copper(I) centres are linked by μ-PO2F2 units [{Cu(xantphos)(μ-PO2F2)} n ] (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) is decribed.Display Omitted
Keywords: Coordination polymer; Copper(I); Hexafluoridophosphate hydrolysis; Crystal structure; P^P chelate; μ-PO2F2 units;

Two new Mn(II) and Co(II) coordination polymers with azide and zwitterionic dicarboxylate ligands L1 and L2 (L1  = [4-((1-carboxylatobenzyl)pyridimium-3-yl) benzoic acid] chloride, L2  = [1,1′-bis(4-carboxylatobenzyl)-4,4′-bipyridinium] dichloride) were synthesized and structurally and magnetically characterized. They are formulated as [Mn3(L1)4(N3)(CH3CH2OH)(H2O)]ClO4·4H2O (1) and [Co3(L2)4(N3)2(H2O)2]·4NO3 (2). Compound 1 contains two different linear trinuclear [Mn3(COO)8(CH3CH2OH)2]2 − and [Mn3(COO)6(H2O)2(N3)2]2 − units built from the mixed bridges of (μ-COO)2(μ 2-Ocarboxylate). The trinuclear units are alternately linked into 1D chains by L1. Compound 2 contains linear trinuclear [Co3(N3)2(COO)4(H2O)2] units built from the mixed bridges (μ-COO)2(μ-H2O). Magnetic studies demonstrated that the mixed triple bridges are antiferromagnetic in compounds 1 and 2.Two new linear Mn(II)3 and Co(II)3 magnetic systems with mixed carboxylate–oxygen bridges derived from two zwitterionic ligands were obtained. The mixed carboxylate–oxygen bridges transmit antiferromagnetic interactions between M(II) ions.Display Omitted
Keywords: Manganese; Cobalt; Zwitterionic dicarboxylate ligand; Magnetic properties;

Atmospheric CO2 capture by a triphenyltin–1,2-bis(4-pyridyl)ethane system with formation of a rare trinuclear carbonato-centered core by Alina-Elena Ghionoiu; Delia-Laura Popescu; Catalin Maxim; Augustin M. Madalan; Ionel Haiduc; Marius Andruh (71-73).
Direct atmospheric CO2 capture occurred during the reactions of triphenyltin chloride (Ph3SnCl) with 1,2-bis(4-pyridyl)ethane (bpa) in methanol and aqueous ammonia. Depending on the reaction temperature, 4 °C and room temperature, two different compounds were obtained: a discrete, trinuclear complex, [(Ph3SnCl)23-CO3)(Ph3Sn)(Hbpa)]·H2O (1), and a coordination polymer 1 [(Ph3SnCl)(Ph3Sn)23-CO3)(bpa)]·H2O (2), respectively. X-Ray crystal structure analysis reveals that both compounds contain a rare trinuclear carbonato-centered core C(OSnPh3)3. The supramolecular architecture of compound 1, assembled by hydrogen-bond interactions, is described.Direct atmospheric CO2 capture occurred during the reactions of triphenyltin chloride (Ph3SnCl) with 1,2-bis(4-pyridyl)ethane (bpa) in methanol and aqueous ammonia, with the formation of two compounds featuring the carbonato-centered core C(OSnPh3)3.Display Omitted
Keywords: Carbon dioxide capture; Organotin(IV); Trinuclear carbonato-centered core; Supramolecular structure;

A complex, [Cd(HL)4](NO3)2 (1) (HL =  β-alanine), was synthesized and characterized by X-ray single crystal diffraction method, which crystallized in an acentric space group Fdd2 with supramolecular diamondoid frameworks and its second harmonic generation (SHG) efficiency has been tested. The ligand in complex 1 is electronically neutral. The counter-ion, NO3 , interacts with β-alanine ligands by asymmetrical H-bonding connections, which induces the structural polarity of complex 1. Based on our understanding of SHG materials, we predicted and found another new SHG material, [ZnL2]n (2) with an acentric space group Cc, although the crystal data of complex 2 has been reported. The possible reasons for complex 2 possessing SHG property were discussed. The analysis about similar and dissimilar influence factors on constructing SHG materials between complex 1 and complex 2 will be useful for synthesizing and finding out more SHG materials.The asymmetrical H-bonding connections in [Cd(HL)4](NO3)2 and flexible molecular conformations of ligands in [ZnL2]n (HL =  β-alanine) are responsible for their polar diamondoid frameworks and SHG properties, respectively.Display Omitted
Keywords: H-bonding diamondoid frameworks; Coordination-bonding diamondoid frameworks; Second harmonic generation (SHG); Supramolecular chemistry;

Two hybrid materials composed of metal-organic framework (JUC-32) nanoparticles and carboxyl-modified multi-wall carbon nanotubes (MWCNTs) were synthesised successfully in situ and characterized by TEM, PXRD, and TGA. The gas adsorption properties of these two hybrid materials were compared with the original JUC-32 material and a physical mixture of JUC-32 and MWCNTs. The results indicated that the composite materials absorbed larger amounts of CO2 and CH4 per specific surface area than the original materials, and that the adsorption enthalpies of CO2 and CH4 had significantly increased.Two hybrid materials composed of metal-organic framework (named JUC-32, JUC = Jilin University, China) nanoparticles and carboxyl-modified multi-wall carbon nanotubes (MWCNTs) were synthesised successfully in situ. And the CO2 adsorption enthalpy of MWCNTs/JUC32-2 was enhanced to 33.8 kJ·mol− 1, compared to 23.4 kJ·mol− 1 for the original JUC-32.Display Omitted
Keywords: Metal-organic frameworks; Carbon nanotube; Hybrid materials; Gas adsorption;

A rare lanthanide-containing azametallacrown with structural formula [Er4(μ 3-OH)2(ppt)4(H2ppt)2(OAc)2]·2DMF (1) (H2ppt = 3-(2-hydroxyphenyl)-5-(pyrazin-2-yl)-1,2,4-triazole) has been reported. X-ray crystallographic analysis exhibits a remarkable aza10-MC-4 structural motif with the ring having [Er–N–N–Er–O] connectivity. Measurements of dc magnetic susceptibility and isothermal magnetization reveal the strong magnetic anisotropy, and ac susceptibility shows slow magnetization relaxation at a dc field of 2000 Oe.Complex 1 shows a rare lanthanide azametallacrown with 10-MC-4 type exhibiting Er–N–N–Er–O connectivity and the cavity encapsulating two μ 3-OH anions. Magnetic measurements reveal strong magnetic anisotropy and SMM behavior.Display Omitted
Keywords: Crystal structure; Triazole-bridging ligand; Lanthanide azametallacrown; SMM behavior;

Complexes with pyrazine-tetrathiafulvalene-dithiolate (pztdt) ligand [M(pztdt)2], M = Ni, Pd, Pt; Synthesis and characterisation by Sandra Rabaça; Sandrina Oliveira; Dulce Belo; Isabel C. Santos; Manuel Almeida (87-90).
The synthesis and characterisation of three metal bisdithiolene complexes based on the recently reported highly extended ligand incorporating fused tetrathiafulvalene and pyrazine moieties, [M(pztdt)2], M = Ni, Pd, Pt and pztdt = pyrazinetetrathiafulvalenedithiolate, are reported. These complexes were obtained under anaerobic conditions as crystals of dianionic tetrabutylammonium salts. The crystal structures of Ni and Pd complexes as determined by single crystal X-ray diffraction confirm the ability of these molecules to established interactions with their neighbours through the pyrazine moieties. These dianionic complexes easily undergo oxidations to their monoanionic and neutral states, with a narrow range of stability for the monoanionic and an extended one for the neutral forms that is rather insoluble in common solvents.Display Omitted
Keywords: Extended bisdithiolene complexes; Nickel; Palladium; Platinum; Pyrazine;

A chiral dysprosium-carboxylate coordination polymer [Dy4(μ 3-OH)4(L)8]n (1) with the 2-(3-chlorophenoxy)propionate (L) ligand has been synthesized and characterized. Four DyIII ions are linked by four μ 3-OH groups to generate a cubic Dy4(μ 3-OH)4 unit, which is further linked by the L ligands to give a one-dimensional (1D) chain based on the cubic Dy4(μ 3-OH)4 secondary building units. Magnetic studies show that 1 exhibits a slow magnetic relaxation under a zero direct-current filed, which is rarely observed for the 1D Dy-based coordination polymers.A one-dimensional chiral dysprosium-carboxylate coordination polymer based on the cubic Dy4(μ 3-OH)4 units has been synthesized. Magnetic studies reveal that the compound exhibits slow magnetic relaxation behavior under a zero direct-current filed.Display Omitted
Keywords: Dysprosium-carboxylate compound; Cubic Dy4(μ 3-OH)4 unit; Magnetization relaxation; Chiral compound;

New open-framework beryllium phosphates with hcb, sql, and bnn topologies by Kangcai Wang; Na Yang; Dingguo Xu; Daibing Luo; Zhien Lin (95-98).
Three new beryllium phosphates, namely, H3aep·Be2(PO4)2(H2PO4)·H2O (1), H2tmdp·Be3(HPO4)3(PO4CH3)·2.25H2O (2), and H2dmpda·Be3(PO4)(HPO4)2(H2PO4) (3), were prepared under solvothermal conditions. These compounds display different open-framework structures with hcb (for 1), sql (for 2), and bnn (for 3) topologies, respectively. The formation of phosphate ester from in situ esterification reaction of phosphoric acid and methanol is noteworthy.Three open-framework beryllium phosphates were synthesized under solvothermal conditions. These compounds display hcb, sql, and bnn topologies. The coexistence of phosphate and methylphosphate in the same crystalline structure is noteworthy.Display Omitted
Keywords: Solvothermal synthesis; Topology; Beryllium; Phosphates; Gas adsorption;

A fluorescent chemosensor for Zn2 + based on 3,8-bis(4-methoxyphenyl)-1,10-phenanthroline by Hui-Fen Qian; Tao Tao; Yue-Hua Wang; Gui Yin; Wei Huang (99-102).
3,8-Bis(4-methoxyphenyl)-1,10-phenanthroline (L) has been found to show high sensitivity toward Zn2 + than other competitive metal ions, where Zn2 +-selective chelation-enhanced fluorescence response at 461 nm is attributed to the formation of a 1:1 metal–ligand complex. In addition, two single-crystal structures of ligand L have been included with the same metal and ligand ratio of 1:1, namely one mononuclear Zn(II) complex [Zn(L)Cl2] (1) and one 1D Cd(II) coordination polymer [Cd(L)(NO3)2]n (2).3,8-Bis(4-methoxyphenyl)-1,10-phenanthroline was found to show high sensitivity toward Zn2 + by forming a 1:1 metal–ligand complex with the Zn2 +-selective chelation-enhanced fluorescence response at 461 nm.Display Omitted
Keywords: Fluorescence; Chemosensor; 1,10-Phenanthroline derivative; Zn(II) complex; Cd(II) complex; Crystal structure;

Hetero-bimetallic 2D coordination network constructed by azacrown ether carboxylic acid with lanthanide(III) and sodium ions by Feifei Su; Junjun Pan; Yanpeng Wei; Lin Fan; Yingchun Liu; Shulan Ma (103-107).
Two lanthanide-based coordination polymers [Na3La(L)Cl·(H2O)6]·NO3 (La-L) and [Na3Eu(L)Cl·(H2O)6]·NO3 (Eu-L) were newly synthesized by reaction of an azacrown ether carboxylic acid ligand H4L (4,7,13,16-tetracarboxymethyl-1,10-dioxa-4,7,13,16-tetraazacyclooctadecane) with La(III)/Eu(III). Complexes La-L and Eu-L exhibited two-dimensional (2D) coordination architectures built up by Ln–L coordinating subunits and one-dimensional (1D) Na–O bridging chains. Four versatile coordination modes of carboxyl groups and Na–O coordination bi-chains linked by novel μ-O bridges (μ2-O and μ3-O) were demonstrated in the structure. Photoluminescence spectra of Eu-L were investigated to reveal characteristic emissions of Eu(III). This is the first example of hetero-bimetallic complex of the tetraazacrown ether ligand with lanthanide and sodium ions.Reaction of carboxyethyl substituted azacrown ether ligand (L) with La(III)/Eu(III) ions produces novel hetero-bimetallic 2D networks which were built up by Ln–L coordinating subunits and 1D Na–O bridging chains.Display Omitted
Keywords: Lanthanide complex; Azacrown ether ligand; Crystal structure; Luminescence;

An unusual 2D nanoscaled quadruple-layer metal–organic framework based on octanuclear cobalt clusters by Hua-Yi Zhang; Xing-Yan Li; Jin-Ling Zhang; Xiao-Lin Chi; Xi-Chi Wang; Xi-Yue Xie; Jiao-Jiao Qiu; Dong-Rong Xiao (108-112).
Self-assembly of a flexible tricarboxylate ligand (H3L) and cobalt salt under hydrothermal conditions yields an unprecedented two-dimensional (2D) nanoscaled quadruple-layer networks [Co4(HL)33-OH)2(H2O)2]·5H2O (1) (H3L = (3,5-dicarboxyl-phenyl)-(4-(2′-carboxyl-phenyl)-benzyl)ether). The structure of compound 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analyses, IR spectrum, and thermogravimetric analysis. Compound 1 represents the first 2D nanoscaled multiple-layer architecture constructed from octanuclear cobalt cluster building blocks. Furthermore, the adjacent sidearm-containing 2D quadruple-layer motifs are interdigitated in a mutual relationship to form a 3D supramolecular framework. In addition, the magnetic properties of compound 1 have been studied by measuring its magnetic susceptibility in the temperature range of 2–300 K, indicating the existence of antiferromagnetic coupling within the octanuclear cobalt cluster.An unprecedented 2D nanoscaled quadruple-layer metal–organic framework, based on centrosymmetric octanuclear Co(II) clusters as secondary building units, is reported, which represents the first example of (2D → 3D) interdigitated network self-assembled from 2D sidearm-containing quadruple-layer motifs.Display Omitted
Keywords: Metal–organic framework; Multiple-layer; Interdigitation; Self-assembly;

Luminescent monomeric and polymeric cuprous halide complexes with 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene as ligand by Fengshou Wu; Hongbo Tong; Kai Wang; Jie Zhang; Zebin Xu; Xunjin Zhu (113-116).
Reaction of cuprous bromide with equimolar amounts of 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) affords a mononuclear three-coordinated complex [CuBr(dpb)] (F2) with dpb acting as a chelating ligand. In contrast, using cuprous iodide instead under the same conditions gives the polymeric compound [Cu2I2(dpb)]n (F1) which contains double-bridging iodine atoms. The complexes were characterized by element analysis and 1H NMR spectroscopy, and the crystal structures were determined by single-crystal X-ray diffraction methods. The Cu(I) complexes are luminescent in the solid state at ambient temperature. Intense orange emission for complex F1 is observed, with maxima at 593 nm, probably ascribed to a combination of a halide-to-metal charge transfer and copper-centered d → s, p transitions. F2 exhibits a blue photoluminescence, with emission maximum at 515 nm, assigned to metal-to-ligand charge-transfer excited states, probably mixed with some halide-to-ligand characters.The preparation, crystal structures, and photophysical properties of two novel coordination compounds, namely [Cu2I2(dpb)]n and [CuBr(dpb)], formed upon reacting copper(I) halides with 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)-benzene (dpb) were reported. Both of the two complexes are photoluminescent in the solid state, and their emissive properties are very dependent on their structures.Display Omitted
Keywords: Cuprous halides; Luminescence; Crystal structures; Coordination polymers;