Inorganic Chemistry Communications (v.14, #7)

Contents List (iii-x).

Tetrameric spin crossover iron(II) complex constructed by imidazole···chloride hydrogen bonds by Koshiro Nishi; Takeshi Fujinami; Aki Kitabayashi; Naohide Matsumoto (1073-1076).
A tetrameric spin crossover (SCO) FeII complex was synthesized, and the structure and magnetic properties were studied. The tetrameric structure is constructed by four imidazole···Cl hydrogen bonds centered at one Cl ion. The compound showed an incomplete gradual SCO behavior due to intra-cluster “anticooperative-like“ interaction.A tetrameric spin crossover (SCO) FeII complex was synthesized, and the structure and magnetic properties were studied. The tetrameric structure was constructed by four imidazole·Cl hydrogen bonds centered at one Cl ion. The compound showed an incomplete gradual SCO behavior due to intra-cluster “anticooperative-like” interactions.Display Omitted► A tetrameric spin crossover (SCO) FeII complex was synthesized. ► The structure and magnetic properties were studied. ► The tetrameric structure is constructed by four imidazole···Cl- hydrogen bonds. ► The compound showed an gradual SCO due to intra-cluster “anticooperative-like“ interaction.
Keywords: Iron; Spin crossover; Hydrogen bond; Imidazole;

Structures and fluorescence properties of two novel metal-organic frameworks based on the bis(2-benzimidazole) and aromatic carboxylate ligands by Luan Jiang; Zong-Xiao Li; Yan Wang; Guo-Dong Feng; Wei-Xing Zhao; Kui-Zhan Shao; Chun-Yi Sun; Lian-Jie Li; Zhong-Min Su (1077-1081).
Two new metal-organic frameworks, [Cd2(H2C3PIm)(BDC)4(H2O)3]n (1) and [Zn3(H2C3PIm)3 (BTC)2(H2O)2]n (2) (H2C3PIm = 2,2′-(1,3-propanediyl)bis(1 H-benzimidazole), H2BDC = 1,4-benzenedicarboxylic acid, H3BTC = 1,3,5-benzene tricarboxylic acid), have been synthesized hydrothermally and their structures are characterized by single crystal X-ray analysis. Compound 1 presents a 1D columnar structure, and compound 2 exhibits a 2D sheet with novel extra-large rings of 4.82 topology. Both complexes exhibit strong photoluminescence at room temperature.Two novel metal-organic frameworks based on the bis(2-benzimidazole), [Cd2(H2C3PIm)(BDC)4(H2O)3]n (1), [Zn3(H2C3PIm)3 (BTC)2(H2O)2]n (2), have been successfully prepared under hydrothermal conditions and characterized. Their fluorescence spectra have been studied, both complexes exhibit strong photoluminescence at room temperature.Display Omitted► Two new interesting Cd(II)-containing and Zn(II)-containing polymeric complexes , [Cd2(H2C3PIm)(BDC)4(H2O)3]n (1) and [Zn3(H2C3PIm)3(BTC)2(H2O)2]n (2) have been prepared. ► 1 presents a 1D columnar structure though three types of coordination modes with Cd ion, while compound 2 exhibits 2D grid structure with novel 32-membered and 64-membere rings of 4.82 topology. ► Both two complexes exhibit strong photoluminescence at room temperature.
Keywords: Hydrothermal synthesis; Bis(2-benzimidazoles); 4.82 Topology; Fluorescence;

Two new three-dimensional (3D) porous metal-organic frameworks, [Ni(tpt)2/3(bpta)1/4(H2O)2(OH)]⋅solve (1) and [Cd(tpt)(H2bpta)]⋅solve (2) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine, H4bpta = (1,1'-biphenyl)-2,2',6,6'-tetracarboxylic acid) have been prepared, and characterized by single-crystal X-ray diffraction, IR spectra, PXRD, and TG analysis. The results show that complex 1 has a 3D bor network structure with 56.9% solvent-accessible volume, and 2 reveals a novol 3,5-coordinated chiral topology with vertex symbol (4.72)(43.62.74.8) and 52.5% accessible void in the structure. Moreover, gas adsorption properties of desolvated 1 and 2 were investigated.Two new three-dimensional (3D) porous metal-organic frameworks, [Ni(tpt)2/3(bpta)1/4(H2O)2(OH)]⋅solve (1) and [Cd(tpt)(H2bpta)]⋅solve (2) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine, H4bpta = (1,1'-biphenyl)-2,2',6,6'-tetracarboxylic acid) have been prepared, and characterized by single-crystal X-ray diffraction, IR spectra, PXRD, and TG analysis. The resulted MOFs reveal highly accessible voids. Moreover, gas adsorption properties of desolvated 1 and 2 were investigated.Display Omitted► Two porous MOFs with new topologies have been synthesized. ► The resulted MOFs reveal highly accessible voids. ► The gas adsorption properties of the reported MOFs have been investigated.
Keywords: Metal–organic frameworks; Crystal structure; Gas adsorption; 2,4,6-Tris(pyridyl)-1,3,5-triazine; (1,1'-Biphenyl)-2,2',6,6'-tetracarboxylic acid;

A novel pillared double-layered Pb(II) coordination polymer based on 1,3,5-benzenetricarboxylic acid and dipyrido[3,2-a:2′,3′-c]-phenazine-2-carboxylic acid by Guang-Bo Che; Jing Chen; Xiang-Cheng Wang; Chun-Bo Liu; Chun-Jie Wang; Shen-Tang Wang; Yong-Sheng Yan (1086-1088).
A fascinating pillared double-layered three-dimensional lead(II) coordination polymer [Pb2(BTC)(DPPZC)]n·2nH2O (1) has been prepared through hydrothermal reaction of lead(II) nitrate with the mixed ligands 1,3,5-benzenetricarboxylic acid (H3BTC) and dipyrido[3,2-a:2′,3′-c]-phenazine-2-carboxylic acid (HDPPZC). The photoluminescent property and thermal stability of 1 were also investigated.An interesting pillared double-layered three-dimensional lead(II) coordination polymer [Pb2(BTC)(DPPZC)]n·2nH2O (1) has been hydrothermally synthesized by the reaction of lead(II) nitrate with the mixed ligands 1,3,5-benzenetricarboxylic acid (H3BTC) and dipyrido[3,2-a:2',3'-c]-phenazine-2-carboxylic acid (HDPPZC).Display Omitted► A pillared double-layered three-dimensional lead(II) complex has been synthesized. ► 1,3,5-Benzenetricarboxylic acid and dipyrido[3,2-a:2′,3′-c]-phenazine-2-carboxylic acid were used as the ligands. ► The Pb(II) complex shows an emission band at 592 nm upon excitation at 365 nm.
Keywords: Lead(II) complex; 1,3,5-Benzenetricarboxylic acid; Dipyrido[3,2-a:2′,3′-c]-phenazine-2-carboxylic acid; Crystal structure;

First transuranium mixed-ligand polyoxometalate complex by Marina N. Sokolova; Grigory B. Andreev; Aleksander B. Yusov (1089-1092).
First mixed-ligand polyoxometalate complex of neptunium, K10.5H0.5[Np(BW11O39)(W5O18)]·15H2O, has been synthesized. Its structure has been determined using X-ray diffractometry and confirmed by electron and IR absorption spectroscopy. The structure consists of [Np(BW11O39)(W5O18)]11− anions, potassium cations and water molecules. The overall symmetry of the [Np(BW11O39)(W5O18)]11− anion can be approximated as C s . Two tetradentate ligands, [W5O18]6− and [BW11O39]9−, are connected to an Np atom through lacunary O atoms, so that a square antiprismatic surrounding of Np is formed.First mixed-ligand polyoxometalate complex of neptunium, K10.5H0.5[Np(BW11O39)(W5O18)]·15H2O, has been synthesized. Its structure has been determined using X-ray diffractometry and confirmed by electron and IR absorption spectroscopy.Display Omitted► First mixed-ligand polyoxometalate complex of transuranium element has been synthesized. ► Crystal structure of K10.5H0.5[Np(BW11O39)(W5O18)]·15H2O has been determined. ► Neptunium atom coordinates two different polyoxometalate ligands
Keywords: Neptunium; X-ray diffraction; Crystal structure; IR spectrum; Electron spectrum; Polyoxometalate;

Synthesis, structure and dielectric properties of two Cr(III)-tetrazole complexes Cr2(2-TPY)4(HO)2 and Cr(2-TPY)2(H2O)Cl by Rui-Jun Xu; Da-Wei Fu; Jing Dai; Yi Zhang; Jia-Zhen Ge; Heng-Yun Ye (1093-1096).
The two compounds Cr2(2-TPY)4(HO)2 1 and Cr(2-TPY)2(H2O)Cl 2 have been synthesized and characterized by single-crystal X-ray crystallography, elemental analysis and IR, (2-TPY = 2-(1  H-tetrazol-5-yl)pyridine). Moreover, their temperature-dependence dielectric constant (ε) measurements of powder and single-crystal samples were performed. The ε of single-crystal sample is twice the ε of powder sample. However, the dielectric loss value (tanδ) of the crystal is relatively small and only half of the tanδ of powder sample. These characteristics were attributed to the higher density level and ordered arrangement of the crystal lattice.Solvothermal treatment of Cr(NO3)3 (or CrCl3) and 2-TPY at 130 °C for two weeks produced the first dinuclear Cr(III)-tetrazole coordination compound 1. And 2 is a hex-coordinated mononuclear complex. The compounds 1 and 2 showed interesting dielectric constant properties at a relatively high frequency of 1 M Hz.Display Omitted► Compound 1 was the first dinuclear Cr(III)-tetrazole crystal. ► The dielectric properties of Cr(III) complexes have been studied for the first time. ► The crystal samples to compounds 1 and 2 showed interesting dielectric properties.
Keywords: Cr(III) complex; Crystal structure; Dielectric constant; Ordered arrangement; Tetrazole;

Three new complexes synthesized from an imidazole-based dicarboxylate ligand containing hydroxymethyl group by Sheng-Run Zheng; Song-Liang Cai; Jun Fan; Tian-Tian Xiao; Wei-Guang Zhang (1097-1101).
Three new complexes, [Cd(H2hmIDC)(bpy)]n (1), {[Co4(HIDC)4(bpy)4]·14H2O}n (2) and {[Co5(IDC)2(HIDC)2(phen)4(H2O)2]·12H2O}n (3) (H4hmIDC = 2-(hydroxymethyl)-1 H-imidazole-4,5-dicarboxylic acid, H3IDC = imidazole-4,5-dicarboxylic acid, bpy = 2,2’-bipyridyl, phen = 1,10-phenanthroline), were obtained under hydrothermal conditions by using H4hmIDC as initial reactant. Complex 1 is a zigzag chain containing angular [Cd(phen)]2+ node and H2hmIDC2- linker, compound 2 is a discrete Co4 square, while 3 is a 1D chain based on Co4 square motifs similar to that in complex 2. In complex 1, the hydroxymethyl group of the H4hmIDC molecule retains integrated and acts as effective hydrogen bonding interaction site, while in complexes 2 and 3, all the hydroxymethyl groups are lost in situ. The hydroxymethyl groups undergo different reactions directed by metal ions.The hydroxymethyl group of the imidazole-based dicarboxylate ligand undergo different reactions directed by metal ions.Display Omitted►The imidazole-based dicarboxylate ligand containing hydroxymethyl group. ►The ligand undergoes different reactions directed by metal ions. ►The ligand undergoes in situ C–C cleavage reaction. ►A 1D coordination chain based on Co4 squares and Co(II) linker.
Keywords: Imidazole-based dicarboxylate ligand; In situ reaction;

Kinetics and mechanism of oxidation of pyridoxine by enneamolybdomanganate(IV) by S.V. Nipane; V.M. Gurame; G.S. Gokavi (1102-1106).
Oxidation of pyridoxine (vitamin B6) by enneamolybdomanganate (IV) in aqueous perchloric acid medium has been studied spectrophotometrically at 25 °C under pseudo-first-order conditions. The mechanism involves formation of a precursor complex between the reactants which decomposes in a subsequent slow step to give pyridoxal as the intermediate product. The pyridoxal is further oxidized to a final product, 4-pyridoxic acid, by another oxidant molecule in a fast step. The precursor complex formation is supported both kinetically and spectrophotometrically. The accelerating effect of hydrogen ions on the reaction is due to the formation of active hexaprotonated oxidant species. The protonated enneamolybdomanganate(IV) and the pyridoxine cation are found to be the active species of the oxidant and the substrate respectively. The reaction involves direct two-electron transfer step without any free radical intervention. The effects of ionic strength, solvent polarity and the activation parameters were also in support of the mechanism proposed.The mechanism involves a precursor complex formation between the reactants which decomposes in a slow step to give pyridoxal as an intermediate. The final product pyridoxic acid is obtained as a result of rapid oxidation pyridoxal.Display Omitted► The reaction between enneamolybdomanganate(IV) and pyridoxine is found to involve formation of a precursor complex. ► The interaction between the pyridoxine and the oxidant occurs through oxygen atoms non bonded to the central Mn(IV) ion. ► The final product pyridoxic acid was characterised by its characteristic fluorescence spectra. ► A plausible mechanism was proposed and the corresponding rate law was derived.
Keywords: Oxidation; Kinetics; Mechanism; Enneamolybdomanganate(IV); Pyridoxine;

Reaction of Zn(OAc)2·2H2O and bis(2-carboxyethyl)isocyanurate (H3bci) leads to the generation of a new coordination polymer, Zn(Hbci)(H2O)3 (1), (H3bci = bis(2-carboxyethyl)isocyanurate), which features an interesting 2D layer containing Zn(II)–Hbci–Zn(II) right-handed and left-handed helical chains and μ 2-H2O bridges. Furthermore, hydrogen bonds link the adjacent 2D layers to form a 3D supramolecular framework. The photoluminescence property of 1 was also studied.Reaction of Zn(OAc)2·2H2O and bis(2-carboxyethyl)isocyanurate (H3bci) leads to the generation of a new coordination polymer, Zn(Hbci)(H2O)3 (1), (H3bci = bis(2-carboxyethyl)isocyanurate), which features an interesting 2D layer containing Zn(II)–Hbci–Zn(II) right-handed and left-handed helical chains and μ 2-H2O bridges.Display Omitted
Keywords: Coordination polymer; Helical chains; μ 2-H2O bridges; Photoluminescence properties;

The luminescent coordination polymer {[Cd(ita)(bpfp)(H2O)]•4H2O} n (1, ita = itaconate, bpfp = bis(4-pyridylformyl)piperazine) was synthesized via in situ hydrothermal decarboxylation of trans-aconitic acid. [Cd(ita)(H2O)] n undulating chains with gauche conformation ita ligands are connected into a very rare 4-connected 658 layered topology by long-spanning bpfp tethering ligands.The luminescent coordination polymer {[Cd(ita)(bpfp)(H2O)]•4H2O} n (1, ita = itaconate, bpfp = bis(4-pyridylformyl)piperazine) has a very rare 4-connected 658 layered topology, with ita ligands formed by in situ hydrothermal decarboxylation of trans-aconitic acid.Display Omitted► Cadmium coordination polymer with very rare 658 topology 4-connected layer. ► In situ decarboxylation of trans-aconitic acid to form itaconate. ► Ligand-based luminescent properties.
Keywords: Coordination polymer; Cadmium; Crystal structure; Hydrothermal; In situ ligand synthesis;

The reactions of bis(benzothiazol-2-ylethyl)sulfide (bts) and its benzimidazole analogue (btn), both with a N2S-donor atom set, with [Re(CO)5Br] and cis-[ReO2I(PPh3)2] were studied. The X-ray crystal structure of fac-[Re(CO)3(bts)Br] shows that bts acts as a bidentate NS-donor ligand, with a free uncoordinated benzothiazole group. With rhenium(V) the dimer (μ-O)2[Re2O2(btn)2]I2 was isolated, in which btn acts as a tridentate N2S chelate to each metal centre. Each oxo-bridge is unsymmetrical, with unequal Re-O distances.The neutral tridentate ligand bis(benzimidazol-2-yl)sulfide (btn) reacts with oxorhenium(V) cores to produce the di-oxobridge cation (μ-O)2[Re2O2(btn)2]2+.Display Omitted► A rhenium(I) complex with a free benzoxazole group. ► Dimeric oxorhenium(V) complex containing a neutral tridentate ligand. ► Dicationic di-oxo bridged oxorhenium(V) dimer.
Keywords: Rhenium(I); Tridentate benzoxazole; Di-oxo bridged rhenium(V);

Syntheses, structures and photoluminescent properties of two metal-organic complexes assembled with a new polycarboxylate ligand by Chaojun Shen; Tianlu Sheng; Ruibiao Fu; Shengmin Hu; Qilong Zhu; Xiao Ma; Yihui Huang; Xintao Wu (1119-1123).
Two new coordination compounds, [Zn2(HL)(L)(H2O)3]n (1), {[Cd3(L)2(H2O)4]∙H2O}n (2) (H3L = 2,4,6-tri (3-carboxyphenylthio) -1,3,5-triazine), were synthesized hydrothermally and characterized by single-crystal X-ray diffraction. 1 is a 1D wave-like infinite chain which is further connected by hydrogen-bond and noncovalent S…S interactions to form a 3D supramolecular architecture. 2 features 2D layered structure and further forms a 3D supramolecular network based on hydrogen-bond interactions. In addition, both 1 and 2 show strong blue photoluminescence at room temperature resulting from ILCT.Two new coordination polymers have been synthesized under hydrothermal conditions. Intermolecular weak interactions play crucial role in the construction of the two complexes. The structure of complex 1 varies from an infinite 1D chain through 2D nanoporous layer to a 3D network by hydrogen-bond and noncovalent S…S interactions. 2 exhibits a 2D layered framework which is further linked via intersheet hydrogen-bond interactions to form a 3D supramolecular network.Display Omitted► Two new complexes were successfully synthesized by using Zn(II) and Cd(II) ions to react with the ligand H3L under hydrothermal conditions. ► Intermolecular weak interactions such as hydrogen-bond and noncovalent S…S interactions played an important role in constructing 3D supramolecular architecture. ► The two complexes both exhibit strong blue emissions at room temperature, which suggested potential applications in photoluminescent materials.
Keywords: Zn(II) and Cd(II) complexes; Crystal structure; Hydrogen bonds; Noncovalent S…S interactions; Photoluminescent properties;

A new binuclear MoV–DyIII assembly and its magnetism by Shi Ren; Shu-Lin Ma; Gong-Feng Xu; Bin Gu; Yue Ma; Qing-Lun Wang; Dai-Zheng Liao (1124-1127).
The reaction of [Mo(CN)8]3− with Dy3+ in DMF solvent leads to a new binuclear complex, [Mo(CN)8Dy(DMF)4(H2O)3]·H2O (1) (DMF =  N,N′-dimethylformamide). Magnetic measurements confirm that 1 presents probably a ferromagnetic interaction between the binuclear complexes.Construct a binuclear MoV–DyIII complex, in which the coordination sphere of Dy and Mo atoms lie in a slightly distorted trigonal dodecahedron geometry and linked by cyanide group.Display Omitted► Magnetic analysis. ► The magnetic anisotropy of DyIII ion. ► The progressive depopulation of excited Stark sublevels of DyIII ion.
Keywords: Cyano bridge; 4d–4f bimetallic complex; Hydrogen-bond; Spin-orbit coupling;

Heterometallic coordination polymers generated from tripodal metalloligands by Dong-Jiang Li; Li-Qin Mo; Quan-Ming Wang (1128-1131).
Three heterometallic coordination polymers have been prepared by reacting tripodal metalloligand AlL3 (L = 3-(4-pyridyl)acetylacetonate) with MCl2 (M = ZnII, CdII and HgII). The coordination preferences of the metal ions are found to have pronounced effects on the structural topologies. X-ray crystal structural analyses reveal that the complexes display three different kinds of structures. Complex 1 has a distorted ladder-like one-dimensional structure; 2 is a 2D layered structure consisting of rectangular moieties; 3 adopts a helical arrangement.The reactions between tripodal metalloligand AlL3 (L = 3-(4-pyridyl)acetylacetonate) and MCl2 (M = ZnII, CdII and HgII) generate three heterometallic coordination polymers having a distorted ladder-like one-dimensional structure, a 2D layered structure consisting of rectangular moieties, and a helical arrangement, respectively.Display Omitted► Three heterometallic coordination polymers have been prepared. ► Metalloligand AlL3 (L = 3-(4-pyridyl)acetylacetonate) has been used. ► The coordination preferences of metal ions influence the resulted structures.
Keywords: Cadmium; Coordination polymer; Mercury; Metalloligand; Zinc;

Ionothermal synthesis and crystal structure of a magnesium metal-organic framework by Zhao-Feng Wu; Bing Hu; Mei-Ling Feng; Xiao-Ying Huang; Yu-Bao Zhao (1132-1135).
A novel magnesium metal-organic framework formulated as [Amim]2[Mg3(1,4-NDC)4(MeIm)2(H2O)2]·2H2O (1) (Amim = 1-propylene-3-methylimidazolium, 1,4-NDCH2  = 1,4-naphthalene dicarboxylic acid, MeIm = 1-methyl imidazole) was synthesized in an ionothermal reaction by using an ionic liquid 1-propylene-3-methylimidazolium chloride (AmimCl) as solvent and reactant. The coordinated MeIm was in situ produced by the decomposition of AmimCl during the ionothermal synthesis. Single-crystal X-ray analysis reveals that 1 crystallizes in the monoclinic system, space group P21 /n. Its structure is composed of linear trinuclear magnesium clusters as secondary building units and features an anionic three-dimensional (3D) framework with 424·64 topology built upon 8-connected net. The thermal stability of 1 has also been studied.We report on the first example of ionothermal synthesis of magnesium metal-organic framework, namely [Amim]2[Mg3(1,4-NDC)4(MeIm)2(H2O)2]·2H2O (1) (Amim = 1-propylene-3-methylimidazolium, 1,4-NDCH2  = 1,4-naphthalene dicarboxylic acid, MeIm = 1-methyl imidazole) in AmimCl, in which MeIm was in situ produced by thermal decomposition of AmimCl.Display Omitted► The title compound 1 represents the first example of magnesium metal-organic framework prepared in ILs. ► The ligand 1,4-NDCH2 is firstly used to build magnesium metal-organic framework. ► Ionic liquid AmimCl in situ decomposes to produce methyl imidazole as a terminal group coordinated to magnesium atom in compound 1.
Keywords: Ionothermal synthesis; Magnesium; Metal-organic framework; In situ decomposition;

A new dodecanuclear manganese single-molecule magnet from the arrangement of manganese triangles by Ming-Hsuan Liu; Chen-I Yang; Gene-Hsiang Lee; Hui-Lien Tsai (1136-1139).
Bridging-azido ligands are used to create a new dodecanuclear manganese cluster [Mn12O4(salox)12(N3)4(MeOH)6(H2O)2]·5MeOH·2H2O (1·5MeOH·2H2O) from the arrangement of manganese triangles, [Mn3O]. Single-crystal x-ray analysis shows that 1·5MeOH·2H2O contains a [MnIII 12(μ 3-O)4(μ 2-N3)4]24+ core, constructed from four [MnIII 3O]7+ building units, which is a new structural type in the family of Mn12 complexes. Variable temperature magnetic susceptibility and magnetization measurements of the complex 1·5MeOH·2H2O were carried out. The magnetic data indicate that complex 1·5MeOH·2H2O exhibits antiferromagnetic with a non-zero ground state spin value of S  = 4. The frequency dependence of out-of-phase component in alternating current magnetic susceptibility and magnetic hysteresis loop measurements indicate that complex 1·5MeOH·2H2O is a new single-molecule magnet with a significant magnetoanisotropy of U eff  = 70 K.A new dodecanuclear manganese cluster, [Mn12O4(salox)12(N3)4(MeOH)6(H2O)2]·5MeOH·2H2O, is obtained from a reaction of Mn(ClO4)2·6H2O with salicylaldoxime and NaN3. The cluster shows a Mn12 core from the arrangement of four manganese triangles, [Mn3O]. Frequency-dependent AC magnetic susceptibility and magnetic hysteresis loop measurements indicate that the Mn12 cluster is a new single-molecule magnet.Display Omitted► Bridging-azido ligands are used to create a new dodecanuclear manganese cluster. ► Constructed from four [MnIII 3O]7+ building units. ► Complex exhibits antiferromagnetic with a non-zero ground state of S  = 4. ► A new single-molecule magnet with a significant magnetoanisotropy of U eff  = 70 K.
Keywords: Azido bridge; Magnetoanisotropy; Single-molecule magnet; Superparamagnet; Nanoscale magnet;

Two amino-benzotriazole phenol ligands, 2-(2H-benzotriazol-2-yl)-6-((diethylamino)methyl)-4-alkyl-phenol (alkyl = CH3, C1DEA BTP-H, and alkyl = C8H17, C8DEA BTP-H) were prepared through the Mannich condensation of 4-alkyl-2-(2H-benzotriazol-2-yl)phenol with the mixtures of excess paraformaldehyde and diethylamine under reflux conditions. Zinc complexes supported by amino-benzotriazole phenoxide ligands ( C1DEA BTP and C8DEA BTP ) were synthesized and fully characterized. The reaction of ZnEt2 with DEA BTP-H (1 equiv.) produces the tetra-coordinated dimeric zinc complexes [(μ- C1DEA BTP)ZnEt]2 (1) and [(μ- C8DEA BTP)ZnEt]2 (2). Experimental results indicate that complex 1 catalyzes the ring-opening polymerization of ε-caprolactone and β-butyrolactone with good catalytic activities in a controlled character.Zinc complexes supported by amino-benzotriazole phenoxide ligands ( C1DEA BTP and C8DEA BTP ) were synthesized and fully characterized. Complex [(μ- C1DEA BTP)ZnEt]2 (1) catalyzes the ring-opening polymerization of ε-caprolactone and β-butyrolactone in the presence of 9-anthracenemethanol with good catalytic activities in a controlled character.Display Omitted► Zinc complexes bearing the DEA BTP ligand are synthesized and fully characterized. ► Complex 1 catalyzes the polymerization of ε-caprolactone in a “living” fashion. ► Complex 1 catalyzes the polymerization of β-butyrolactone in a “controlled” manner.
Keywords: Zinc complex; Catalyst; N,O-bidentate; Ring-opening polymerization; ε-Caprolactone; β-Butyrolactone;

A new coordination polymer [Ag4(dob)4(BF4)4] (1) was synthesized by reaction of rigid ligand 1,3-di(2-oxazolinyl)benzene (dob) with silver(I) tetrafluoroborate and characterized by elemental analysis, single crystal X-ray diffraction and electrospray mass spectrometry. The complex has one-dimensional (1D) helical chain structure which is further linked together by Ag⋯F and hydrogen bonding interactions to form a three-dimensional (3D) supramolecular structure. Complex 1 crystallizes in the noncentrosymmetrical space group and shows second harmonic generation (SHG) and ferroelectric property.A new helical chain coordination polymer [Ag4(dob)4](BF4)4 (1) was synthesized and found to crystallize in the noncentrosymmetrical space group and show second harmonic generation (SHG) and ferroelectric property.Display Omitted► Coordination polymer with 1,3-di(2-oxazolinyl)benzene. ► Complex with 1D helical chain structure. ► SHG and ferroelectric property of the complex.
Keywords: Silver(I) complex; Helical chain; Noncentrosymmetrical space group; SHG; Ferroelectric property;

Synthesis and crystal structure of (μ4-oxido)hexakis(μ-chlorido)tetrakis(2-(3-pyridyl)ethane-1-ol)tetracopper(II) by Gerard A. van Albada; Mohamed Ghazzali; Khalid Al-Farhan; Jan Reedijk (1149-1152).
A new μ4-oxido-bridged cluster of formula [Cu4(μ-Cl)64-O)L4] (in which L = 2-(3-pyridyl)ethane-1-ol) has been synthesized and fully characterized. The X-ray structure, physical and electronic properties are reported. An unusual network is formed by the hydrogen bond system between the oxygen atoms of the ligand, stabilizing the network structure. A chain-pattern with weak intermolecular interactions along the b axis exists with CuCl–ClCu contacts (3.498 Å) that are marginally shorter than the sum of the van der Waals chloride atomic radii.A new μ4-oxido-bridged cluster of formula [Cu4(μ-Cl)64-O)L4] (with L = 2-(3-pyridyl)ethane-1-ol) is reported; less common intermolecular O–H–O hydrogen bonds between 4 clusters stabilize the structure.Display Omitted► A new oxide- and chloride-bridged tetranuclear Cu(II) compound has been prepared. ► The hydroxyl groups form intermolecular hydrogen bonds stabilizing the structures. ► Structure shows uncommon hydrogen bonds between 4 clusters and short Cl–Cl contacts. ► The 3-hydroxyethylpyridine binds with pyridine nitrogen to Cu.
Keywords: Copper; Hydrogen bonding network; Halogen–halogen interaction;

Absorption and luminescence spectra of cochineal by Horst Kunkely; Arnd Vogler (1153-1155).
Carminic acid which can be obtained as extract (cochineal) from certain scale insects is an important red dye with many applications. It shows a red fluorescence under ambient conditions. The lowest-wavelength absorption and the corresponding emission undergo a red shift when carminic acid interacts with metal cations such as Zn2+, Al3+, Gd3+ and Th4+ in aqueous solution. The Al3+ complex of carminic acid which is isolated as Ca2+ salt (carmine) displays this fluorescence also in the solid state while the Ni2+ complex is not luminescent under any conditions owing to the presence of low-energy ligand field states.Carminic acid is a natural red dye which can be isolated as cochineal. It is traded in two forms: cochineal as carminic acid with organic by-products and carmine which is the Ca2+ salt of the aluminium complex of carminic acid. Generally, metal cations such as Zn2+, Al3+, Ni2+, Gd3+ and Th4+ can be attached to carminic acid in aqueous solution. The absorption and emission spectra of these complexes have been recorded and discussed.Display Omitted► In the presence of various metal salts carminic acid interacts with metal cations such as Zn2+, Al3+ (carmine), Ni2+, Gd3+ and Th4+. ► These metal complexes display long-wavelength absorptions in the visible region and with the exception of Ni2+ a fluorescence which provides a general analytical access to this class of compounds.
Keywords: Coordination chemistry; Aluminum; Carminic acid; Absorption spectra; Luminescence spectra;

Two new coordination frameworks, namely, [Zn2(aip)(Haip)2(H2O)2]⋅2H2O (1) and [Cu2(aip) (H2O)(μ3-OH)2] (2),were synthesized from the corresponding metal salts with 5-aminophthalic acid (H2aip) under hydrothermal conditions. They possess interesting 3D architectures constructed from the rod-shaped secondary building blocks with 5-nodal (3, 4, 5, 6)-connected and (3, 5, 6)-connected network topologies, respectively. Moreover, luminescent behaviors of two complexes have been investigated at room temperature and they show the intense blue emissions.Two new 3D coordination polymers possess 3D architectures constructed from the rod-shaped SBUs with 5-nodal network topologies as well as show the intense blue emission at room temperature.Display Omitted► Two complexes 12 are assembled by 1D rod-shaped secondary building blocks. ► They show 3D metal-organic frameworks with 5-nodal network topologies. ► They have different topologies, due to multiple coordination modes of aip anions.
Keywords: 5-Aminoisophthalate; Metal-organic framework; Rod-shaped secondary building blocks; Synthesis; Luminescence;

Ru(II) xantphos complex as an efficient catalyst in transfer hydrogenation of carbonyl compounds by Ali Nemati Kharat; Abolghasem Bakhoda; Bahareh Tamaddoni Jahromi (1161-1164).
In the transfer hydrogenation of aromatic/aliphatic carbonyl compounds using iso-propanol–potassium hydroxide mixture as hydrogen donor, a mixed ligand Ru(II) complex, prepared from xantphos ligand and RuCl2(dmso)4, was examined. Besides, the solid state structure of the Ru (II) complex was determined using X-ray single crystallography. The catalytic reactivity of the complex was remarkable (up to 99%) and the catalyst showed more efficiency in the reduction of ketones than aldehydes.Display Omitted► [Ru (P,O,P-xantphos) (S-dmso) Cl2], 1, was synthesized by simple procedures. ► Structure of 1 was determined by X-ray crystallography. ► 1 was tested in transfer hydrogenation of carbonyl compounds.
Keywords: Ruthenium complex; Xantphos; Transfer hydrogenation; X-ray crystallography; Hydrogen bonding; C―H…π interaction;

Lanthanide metal organic frameworks based on octahedral secondary building units: Structural, luminescent, and magnetic properties by Hua-Bin Zhang; Yan Peng; Xiao-Chen Shan; Chong-Bin Tian; Ping-Lin; Shao-Wu Du (1165-1169).
Three new lanthanide metal organic frameworks (LnMOFs), [HNMe2][Ln2(m-BDC)3(phen)2] (Ln = Eu 1, Gd 2, Tb 3, m-H2BDC = 1,3-benzenedicarboxylic acid, phen = 1,10-phenanthroline), have been solvothermally synthesized through self-assembly reactions. Complexes 13 are isostructural and possess 3D architectures based on the octahedral [Ln2(COO)6] SBUs with a pcu net topology. Photoluminescence measurements show that 1 and 3 are highly emissive at room temperature with quantum yields of 86.87% (at 330 nm) and 85.62% (at 345 nm), respectively, and may be good candidates for light-emitting diodes (LEDs) and light applications. The magnetic properties of 2 and 3 have also been investigated through the measurement of their magnetic susceptibilities over the temperature range of 2–300 K.Three new 3D LnMOFs have been synthesized employing mixed ligands of 1,3-benzenedicarboxylic acid and 1,10-phenanthroline. The frameworks are based on octahedral secondary building units with pcu topological net. Luminescent and magnetic properties have been examined in the solid stateDisplay Omitted► High performance in quantum yields (>85%) and fluorescence lifetime for 1 and 3. ► Pcu net topology frameworks based on octahedral secondary building units. ► Magnetic interaction between Gd(III) ions can be estimated by a simple dimeric mode. ► Mixed ligand complex.
Keywords: Pcu net topology; Lanthanide complexes; Luminescent property; Magnetic property;

A new coordination polymer [Cd2(cpta)(H2O)4]n (1) (H4cpta = cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid) has been hydrothermally synthesized and structurally characterized by IR, elemental analysis and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 is a six-connected pcu-type network with (41263) topology. 1 also displays strong fluorescent emissions in the solid state at room temperature.A new 3D 6-connected coordination polymer with 41263 topology, [Cd2(cpta)(H2O)4]n (H4cpta = cis,cis,cis-1,2,3,4-cyclopentanetetra carboxylic acid), has been synthesized under hydrothermal synthesized using H4cpta as linear linkers and Cd4-clusters as 6-connected nodes.Display Omitted► Recently, a large number of organic ligands as potential linkers, polynuclear coordination polymers consisting polycarboxylate ligands have witnessed the most important development. ► To the best of our knowledge, complexes based on cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic ligand have rarely been reported, maybe due to its versatility and flexibility in binding fashions when forming coordination architectures, although the rigid tetracarboxylate ligand, benzene-1,2,4,5-tetracarboxylic acid, has been widely investigated. ► In this study, we select cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid considering its following several feature: (a) it has four carboxyl groups that provide versatile binding fashions; (b) In view of the number of deprotonated carboxyl groups, it can behave not only as hydrogen-bond acceptor but as hydrogen-bond donor; (c) It connects the metal ions in various directions, because all carboxyl groups do not lie in one plane. In this paper, we report the synthesis, crystal structure, and photoluminescence of a new [Cd2(cpta)(H2O)4]n(1), which features an interesting 3D coordination polymer.
Keywords: Coordination polymer; Cluster compound; Hydrothermal synthesis; Luminescence properties;

An interdigitated 3D framework with 5-connected BN topology by Cun-Kuan Wang; Yan Zhou; Lan-Ping Xu; Lei Han (1174-1177).
A flexible coordination polymer 1 with interdigitated structure has been synthesized from 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) ligand and Cd2+ salt, whose 3D interdigitated framework displays novel 5-connected BN topology involving both covalent and strong hydrogen bonds. The luminescent properties of 1 are discussed.A flexible 3D interdigitated coordination framework was mutually assembled from 2D layer with strong hydrogen bonds, which gives novel 5-connected BN topology.Display Omitted► The coordination polymer displays interdigitated structure. ► The 3D framework exhibits 5-connected BN topology involving both covalent and hydrogen bonds. ► The luminescent and thermol properties of compound are investigated.
Keywords: Coordination polymer; Interdigitated framework; BN topology; 4,4′-(hexafluoroisopropylidene)bis(benzoic acid);

A novel organic–inorganic hybrid dimeric arsenotungstate [enH2]4{[Cu(en)2][(A-β-H2AsW9O34)Cu(en)2]2}·8H2O (1) has been prepared by reaction of Na8[A-α-HAsW9O34]·11H2O with CuCl2·2H2O and ErCl3 in the presence of ethylenediamine (en) under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The skeleton of 1 exhibits an interesting centric dimeric structure formed by two opposite trivacant Keggin [(A-β-H2AsW9O34)Cu(en)2]5− subunits linked by a [Cu(en)2]2+ connector, which represents a rare organic–inorganic hybrid arsenotungstate consisting of [A-β-AsW9O34]9− fragments. Interestingly, the trivacant Keggin precursor [A-α-AsW9O34]9− has been isomerized to the trivacant Keggin fragment [A-β-AsW9O34]9− in 1 under hydrothermal conditions. The photocatalytic measurement illustrates that 1 can effectively inhibit the photodegradation of rhodamine-B.A novel organic–inorganic hybrid dimeric arsenotungstate [enH2]4{[Cu(en)2][(A-β-H2AsW9O34)Cu(en)2]2}·8H2O has been prepared, which can effectively inhibit the photodegradation of rhodamine-B.Display Omitted► Organic–inorganic hybrid dimeric arsenotungstate. ► The hybrid arsenotungstate consisting of [A-β-AsW9O34]9− fragments. ► The hydrothermal isomerization of [A-α-AsW9O34]9− to [A-β-AsW9O34]9−.► The photodegradation of rhodamine-B.
Keywords: Polyoxometalate; Arsenotungstate; Copper; Trivacant Keggin structure;

A novel europium(III)–imidazol–diketonate–phenanthroline complex as a red phosphor applied in LED by Huihui Wang; Pei He; Haigang Yan; Jianxin Shi; Menglian Gong (1183-1185).
A β-diketone, 4-imidazol-4,4,4-trifluorobutane-1,3-dione (HIDTFBD) and the corresponding europium(III) complex Eu(IDTFBD)3phen were designed and synthesized, where phen was 1,10-phenanthroline. The complex was characterized by IR, UV–visible, thermogravimetric analysis (TGA) and photoluminescence (PL) spectroscopy. Monitored at 610 nm, the Eu(III) complex exhibited a strong and wide excitation band between 320 and 420 nm due to the formation of a big π-conjugated system in the complex molecule. Under near UV-light excitation, the complex showed strong red emission of Eu3+ ion due to the 5 D 07 F J (J  = 0–4) transitions. The fluorescence lifetime and the luminescence quantum yield were also measured. Finally, a bright red light-emitting diode was fabricated by coating the europium ternary complex onto an ~ 395 nm-emitting InGaN chip, and the LED exhibited appropriate CIE chromaticity coordinates in red area. All these results suggest that the Eu(III) complex is a promising candidate as red component for fabrication of near UV-based white light-emitting diodes.A β-diketone, HIDTFBD, and the corresponding europium(III) complex Eu(IDTFBD)3phen were designed and synthesized. Bright red light-emitting diodes were fabricated by coating the complex onto ~ 395 nm-emitting InGaN chips. All these results suggest that the complex is a promising candidate as red component for fabrication of NUV-based white light-emitting diodes.Display Omitted► A β-diketone, 4-imidazol-4,4,4-trifluorobutane-1,3-dione (HIDTFBD) and the corresponding europium(III) complex Eu(IDTFBD)3phen were designed and synthesized, and the complex was first used on LED. ► The Eu(III) complex exhibited strong red emission of Eu3+ ion due to the 5 D 07 F J (J  = 0–4) transitions under the ~ 395 nm excitation. ► The photoluminescence mechanism of the Eu(III) complex was proposed as a ligand-sensitized luminescence process (antenna effect). ► Bright red light-emitting diodes were fabricated by coating the europium ternary complex Eu(IDTFBD)3phen onto ~ 395 nm-emitting InGaN chips, and the LEDs exhibited appropriate CIE chromaticity coordinates in red area.
Keywords: β-diketone; Eu(III) complex; Phosphor; Luminescence; LED;

In the compound [Pb2(L)2(1,4-bdc)2]n (1), each Pb(II) atom is seven-coordinated by two nitrogen atoms from one L ligand, and five carboxylate oxygen atoms from three different 1,4-bdc ligands in a distorted monocapped triangular prismatic coordination geometry (1,4-bdc = 1,4-benzenedicarboxylate and L  = dipyrido[7,6-a:6′,7′-c]-3-chloropyrido[2,3-b]quinoxaline). The Pb(II) atoms are connected together by the 1,4-bdc ligands to form a 2D network with large windows. The dangling L ligands of each layer are threaded into the voids of the two adjacent layers above and below, thus every window of each layer is threaded by only two dangling ligands that come from opposite directions. Finally, this unique simultaneous threading fashion of adjacent polymeric motifs gives the novel 2D → 3D polythreading array. In addition, the strong π–π interactions between the L ligands and the 1,4-bdc ligands of neighboring layers make great contribution to the structural stabilization of 1.A new coordination polymer has been synthesized by using a long 1,10-phenanthroline derivative ligand and a dicarboxylate ligand under hydrothermal condition, which represents an unusual example of 2D → 3D polythreaded system.Display Omitted► We reported a coordination polymer based on a 1,10-phenanthroline derivative ligand. ► The compound shows a polythreading coordination motif. ► Also, the compound reported here represents an unusual example of 2D → 3D polythreading system.
Keywords: Coordination polymer; Polythreading; Dipyrido[7,6-a:6′,7′-c]-3-chloropyrido[2,3-b]quinoxaline; Topology;