Inorganic Chemistry Communications (v.16, #C)

Contents (iii-ix).

A phosphorescent chemosensor for Cu2 + based on cationic iridium(III) complexes by Hong Yang; Yachao Zhu; Liutao Li; Zhiguo Zhou; Shiping Yang (1-3).
A cationic phosphorescent iridium complex 1 was synthesized, which can selectively detect Cu2 + confirmed by the luminescence spectra titration. In the presence of Cu2 +, the obvious decrease of the luminescence intensity at 600 nm was investigated. The complex has been shown to display high selectivity for Cu2 + over other metal ions. The strong selective coordination interaction with Cu2 + is responsible for the significant change of the luminescence spectra, which is further confirmed by ESI-MS.A cationic phosphorescent iridium complex 1 was synthesized for the detection of Cu2 +.Display Omitted► A cationic phosphorescent iridium complex was synthesized. ► The complex can used as a highly selective “turn-off”-type chemosensor for Cu2 +. ► The 1:1 stoichiometry between the complex and Cu2 + was confirmed by ESI-MS.
Keywords: Copper ion; Iridium complex; Phosphorescence; Chemosensor;

A new approach to the luminescent thin films deposition of non-volatile and non-soluble lanthanide aromatic carboxylate, based on the formation and decomposition of mixed-ligand complexes, was proposed and exemplified for terbium o-phenoxybenzoate thin film deposition.Thin films of non-soluble lanthanide aromatic carboxylates Ln(Carb)3 can be deposited from the solution in three steps: 1. soluble mixed-ligand complex (MLC) formation, 2. MLC thin film deposition and 3. MLC thermal decomposition with formation of Ln(Carb)3 thin film.Display Omitted► Terbium o-phenoxybenzoate dissolved via the mixed-ligand complex (MLC) formation. ► Thin film of MLC was deposited. ► Neutral ligand was removed from the MLC film to form terbium o-phenoxybenzoate film.
Keywords: Lanthanides; Aromatic carboxylates; Luminescence; Thin films; Solution deposition; Complexes;

Three new coordination polymers, [M1.5(stp)(bpe)(H2O)] (M = Mn(1), Cd(2), Zn(3)) have been prepared by hydro-/solvo-thermal reactions of 2-sulfoterephthalate (stp) and 1,2-bis(4-pyridyl)ethane (bpe) ligands with d-block Mn(II), Cd(II) and Zn(II) salts. Complexes 1 and 2 are isomorphic except for the difference of the metal ions, while complexes 13 are polymorphic because of the different coordination modes that stp ligand adopts. The left- and right-handed helixes construct 2D layer from metal ions and stp ligands for 13, and the anti-bpe ligands as the pillars complete 3D structure. All the three complexes exhibit a new (2,3,4)-connected network with the Schläfli symbol {8;122}4{82; 12; 142; 16}{8}2 based on the different structural motifs. The magnetic properties of 1 reveal that there exists weak antiferromagnetic coupling between the Mn(II) ions. And the solid-state photoluminescence of 2 and 3 can be attributed to the intraligand π–π* transition.Three metal–organic frameworks with 2,3,4-connected {8;122}4{82; 12; 142; 16}{8}2 topology are described, in which the left- and right-handed helixes construct 2D layer from metal ions and stp ligands and the anti-bpe ligands as the pillars complete 3D structure. Complexes 1 and 2 are isomorphic, while complexes 13 are polymorphic.Display Omitted► We report three 3D bpe-pillared layer structures from nblock metal and stp. ► M2 +, stp and bpe form a 2,3,4-connected {8;122}4{82; 12; 142; 16}{8}2 topology. ► Left- and right-handed helixes construct the 2D layer of M2 + and stp. ► Mn and Cd complexes are isomorphic, and polymorphic with Zn complex.
Keywords: Hydro-/solvo-thermal synthesis; Crystal structure; Isomerism;

Silver(I) coordination polymers, [Ag(bpba)(CF3SO3)]·0.5CH3CN (1) and [Ag2(bpba)2(NO3)2]·CH3CN·H2O (2) with bis(4-pyridyl)benzylamine (bpba) have been prepared and structurally characterized. 1 shows two-dimensional structure formed by the offset π–π stacking interactions between ladder-like chains, whereas 2 displays three-dimensional network linked by one-dimensional chains with 8-shaped. Different from 1, 2 appears a strong visible emission ranging from 450 to 550 nm.Novel silver(I) coordination polymers with bis(4-pyridyl)benzylamine have been prepared and structurally characterized. 1 shows two-dimensional structure containing ladder-like chains, whereas 2 displays three-dimensional network linked by one-dimensional chains with 8-shaped. In particular, 2 appears a strong visible emission ranging from 450 to 550 nm.Display Omitted► Novel functional ligand, bis(4-pyridyl)benzylamine, is prepared and characterized. ► Multidimensional silver(I) coordination polymers (1 and 2) have been prepared and characterized. ► The X-ray single-crystal structures of 1 and 2 are obtained and analyzed in detail. ► The photoluminescent properties of 1 and 2 are measured and analyzed in detail.
Keywords: Coordination polymer; Silver(I) compound; Ligand; Crystal structure; Photoluminescence;

A new 2D gallium metal–organic framework formulated as Ga(OH)(BPDA) (1) (H2BPDA = 2,4′-biphenyldicarboxylic acid, C14O4H10) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, infrared (IR) spectroscopy, thermal gravimetric analysis (TGA) and luminescence studies. The neutral layer structure of the coordination polymer 1 is constructed from GaO4(OH)2 octahedra and organic BPDA2- linkers, with the parallelogram tunnels joined through one-dimensional ―OH―Ga―OH― chains. Complex 1 exhibits intense green-blue emission at 482 nm (λ ex  = 329 nm) in the solid state at room temperature.A new 2D gallium-2,4′-biphenyldicarboxylate layer with (6,4) topological structure and parallelogram tunnels.Display Omitted► A new gallium layer structure with parallelogram tunnels. ► The 2D layer displays (6,4) topological structure. ► The complex exhibits intense green-blue emission at room temperature.
Keywords: Gallium; Metal–organic framework; Hydrothermal synthesis; Crystal structure;

A new luminous end-to-end thiocyanato bridged heptacoordinated coordination polymer of lead(II) containing a tetradentate Schiff base by Soumi Chattopadhyay; Kishalay Bhar; Somnath Choubey; Sumitava Khan; Partha Mitra; Barindra Kumar Ghosh (21-24).
A new end-to-end thiocyanato bridged coordination polymer [Pb(enbzpy)(μ1,3-NCS)(NCS)]n (1) has been synthesized using a one-pot reaction of Pb(OAc)2.3H2O, tetradentate Schiff base N,N΄-(bis(pyridine-2-yl)benzylidene)ethane-1,2-diamine (enbzpy) and NH4NCS in MeOH solution at room temperature. Single crystal X-ray diffraction measurement reveals that each lead(II) adopts a pentagonal bipyramidal geometry with a PbN6S chromophore coordinated through four N atoms of enbzpy, two μ1,3-bridged N and S atoms and one terminal N atom of thiocyanates. In crystalline state, 1 forms a 2D honeycomb like (63) topology through S∙∙∙S interaction and the layers stack through face-to-face π∙∙∙π interaction giving rise to a 3D network. At room temperature DMF solution of 1 displays a high-energy intraligand 1(π-π*) fluorescence.Synthesis, structure and luminescence property of an 1D coordination polymer [Pb(enbzpy)(μ1,3-NCS)(NCS)]n (1) is described in which 2D honeycomb like (63) topology through S∙∙∙S interaction is formed, and the layers stack through π∙∙∙π interaction giving rise to a 3D network.Display Omitted► One μ1,3-thiocyanato bridged 1D coordination polymer of lead(II) is isolated. ► X-ray study reveals interesting 2D honeycomb like (63) topology through S∙∙∙S interaction. ► The compound with the tetradentate Schiff base is example of luminous material. ► Thermogravimetric analyses show their thermal stability and decomposition pattern.
Keywords: Heptacoordinated lead(II) polymer; Schiff base; Thiocyanate bridge; S∙∙∙S interaction; Luminescence;

Boosting the sensitivity of pH responsible luminescent switches of polypyridyl ruthenium(II) complexes by structural design by Feng Gao; Xing Chen; Qian Sun; Jia-Ning Cao; Jin-Qiang Lin; Qi-Zhi Xian; Liang-Nian Ji (25-27).
A series of novel polypyridyl ruthenium(II) complexes with two 4,7-diphenyl-1,10-phenanthroline (dip) and one 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline (pip) or its analogs have been designed to act as pH responsible luminescent switches through protonation of the imidazole-containing pip ligands in aqueous solution at room temperature. The complex containing methoxyl group showed an on–off ratio of 110 that is higher than any reported pH light switch. This extraordinary high sensitivity is attributed to both the higher LUMO energy level and the electronic donating property of methoxyl group.Four novel polypyridyl ruthenium(II) complexes have been synthesized. The complex containing methoxyl group showed an extraordinary high sensitivity than any reported pH responsible luminescent switch, which is attributed to both the higher LUMO energy level and the electronic donating property of methoxyl group.Display Omitted► Four new polypyridyl Ru(II) complexes were synthesized and characterized. ► pH responsible luminescent switch property have been studied. ► Structures–sensitivity relationship has been concluded.
Keywords: Ruthenium(II) complex; Protonation; Luminescent pH switch;

Two novel lanthanide–copper complexes with an unprecedented μ7-edta coordination mode have been synthesized and characterized by single-crystal X-ray diffraction studies. Its framework can be described as one 2D net with Cu(edta)(H2O) as the edges and Cu2(H2O)2 as the nodes and the lanthanide atom is captured in the center.Display Omitted► Two novel lanthanide-copper complexes with EDTA ligand have been synthesized. ► Its 2D net can describe the edges of Cu(edta)(H2O) and the nodes of Cu2(H2O)2. ► One lanthanide ion is captured in each mesh. ► The edta4 − ligand acts as a hendecadentate bridging ligand.
Keywords: EDTA; Copper; Lanthanide; Crystal structure; Magnetic properties;

1D Metal-Pyrimidine chain with antiferromagnetic coupling and spin-canting behavior by Li Jia; Jin-Cheng Xie; Juan Zhang; Hao-Ling Sun; Zhaofei Li (33-36).
Two isostructural compounds [M(hpmc)(phen)(H2O)] [M = Mn (1), Co (2); H2hpmc = 6-hydroxypyrimidine-4-carboxylic acid, phen = 1,10-phenanthroline] were synthesized by the in-situ hydrothermal reactions of 6-chloropyrimidine-4-carboxylic acid (Clpmc) with MnII and CoII ions, in which the metal centers are bridged by pyrimidine ring to form 1D chain. Magnetic studies indicate pyrimidine can transmit antiferromagnetic coupling and the CoII complex shows spin-canting behavior below 3.5 K.By in-situ hydrothermal reaction of 6-chloropyrimidine-4-carboxylic acid (Clpmc) with MnII and CoII ions, two isostructural pyrimidime-bridged 1D chain compounds [M(hpmc)(phen)(H2O)] [H2hpmc = 6-hydroxypyrimidine-4-carboxylic acid, phen = 1,10-phenanthroline] were firstly synthesized. Magnetic studies indicate pyrimidine can transmit antiferromagnetic coupling and the CoII complex shows spin-canting behavior below 3.5 K.Display Omitted► Compounds 1 and 2 are the first examples of complexes bridged by 6-hydroxypyrimidine-4-carboxylic acid (H2hpmc). ► In-situ generation of 6-hydroxypyrimidine-4-carboxylic acid from 6-chloropyrimidine-4-carboxylic acid is firstly reported. ► The variable-temperature magnetic data indicate that pyrimidine ring in hpmc ligand transmits antiferromagnetic coupling in both 1 and 2. ► Compared with 1, 2 also shows spin-canting behavior due to the anisotropy of Co(II) ions. ► The fact that compounds of 1 and 2 with similar structure show different magnetic behavior varying with the magnetic anisotropy of spin carrier conduces to establish suitable model for understanding the influence of magnetic anisotropy on the final magnetic behavior of two isostructural compounds.
Keywords: Pyrimidine carboxylic acids; Crystal structure; Magnetism; Spin-canting;

Colorimetric and fluorescence turn-on sensor for biologically important anions based on carbazole derivative by Xuefang Shang; Xinjuan Li; Jie Han; Shenyu Jia; Jinlian Zhang; Xiufang Xu (37-42).
A colorimetric and fluorescent anion chemosensor containing carbazole group has been designed and synthesized based on photoinduced electron transfer (PET). The strong basic anions such as F, AcO and H2PO4 resulted in significant red-shift in absorption band and enhancement in fluorescent emission intensity of the compound 1, synchronously accompanied by a “naked eye” color change from light yellow to orange-yellow in organic medium. The determination limit of sensor 1 toward H2PO4 is 1.0 × 10− 6  mol·L− 1. 1H NMR titration experiments shed light on the nature of the interaction between 1 and the anions. Theoretical investigation further illustrated the possible binding mode of host–guest and the roles of molecular frontier orbitals in anion binding.A colorimetric and fluorescent anion chemosensor based on carbazole derivative has been designed and synthesized based on photoinduced electron transfer (PET). The strong basic anions such as F-, AcO- and H2PO4 - resulted in significant red-shift in absorption band and increase in fluorescent emission intensity of the compound, synchronously accompanied by a “naked eye” color change from light yellow to orange-yellow in organic medium. The determination limit of sensor 1 toward H2PO4 is 1.0 × 10− 6  mol·L− 1. Theoretical investigation further illustrated the possible binding mode of host–guest and the roles of molecular frontier orbitals in anion binding.Display Omitted► Colorimetric and fluorescence turn-on sensor based on carbazole derivative. ► The interacted mechanism based on photoinduced electron transfer (PET). ► The red-shift in absorption band and increase in emission intensity for H2PO4 . ► The determination limit of the sensor toward H2PO4 is 1.0 × 10− 6  mol·L− 1. ► The roles of molecular frontier orbitals in anion binding.
Keywords: Colorimetric sensor; Fluorescence; PET; Naked-eye; Carbazole; Determination limit;

A non-interpenetrating 3D porous metal-organic framework (MOF) holding rutile-type topology containing Cu4 secondary building units by Gong-ming Sun; Xue-feng Feng; Hai-xiao Huang; Zhen-wei Liao; Yu-mei Song; Xiao-zhao Tian; Shu-juan Liu; Feng Luo (43-46).
In this work, we obtained a rarely three-dimensional porous Cu(II) MOF, namely [Cu2(BTC)(OH)(Me2NH)⋅ 2H2O ⋅ DMF] n (Me2NH—dimethylamine, [BTC3 −—1,3,5-benzenetricarboxylate, DMF—N,N′-dimethylformamide], by solvo(hydro)thermal method. This polymer was characterized by single-crystal X-ray diffraction, EA, and thermogravimetry analysis. The outstanding structural feature of it is the coordination of Me2NH—a hydrolysate from DMF, and the non-interpenetrating porous rutile net. Further, based on the investigation of literatures, we also discussed the architectonics involving common Cu4 secondary building unit (SBU) in detail.We obtained a rarely three-dimensional porous Cu(II) MOF by solvo(hydro)thermal method. The outstanding structural features of it are the coordination of Me2NH—a hydrolysate of DMF, and the non-interpenetrating porous rutile net.Display Omitted► Presented here is a non-interpenetrating porous rutile net. ► The special Me2NH coordination is notable. ► The Cu4 SBU is discussed in detail.
Keywords: Porous MOFs; Cu4 secondary building units; Rutile; Solvo(hydro)thermal method;

Three new zinc(II) complexes Zn(L1)2 (1), Zn2L2(OAc)3 (2) and Zn2L3(OAc)3 (3) have been synthesized by using Zn(OAc)2·2H2O and potentially multidentate Schiff base ligands HL1 (2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol), HL2 (2-((1-hydroxy-2-methyl-propan-2-ylimino)methyl)-6-methoxyphenol) and HL3 (2-((2-hydroxypropylimino)-methyl)-6-methoxyphenol), respectively. These Schiff base ligands are the condensation product of o-vanillin and corresponding amino alcohols. All the three complexes 1, 2 and 3 have been characterized by elemental analysis, IR, single crystal X-ray diffraction and fluorescence studies. Structural studies reveal that 1 is a mononuclear complex whereas in dinuclear complexes 2 and 3 the two Zn(II) centers are held together by deprotonated Schiff base ligands and acetates. All the synthesized complexes display intraligand (π → π*) fluorescence and can potentially serve as photoactive materials.Three blue luminescent zinc(II) complexes have been synthesized by using Zn(OAc)2·2H2O and potentially multidentate Schiff base ligands. The structures of all the three complexes 1, 2 and 3 have been determined by single crystal X-ray diffraction.Display Omitted► Three zinc(II) complexes with blue luminescent which display intraligand (π → π*) fluorescence has been synthesized. ► The fluorescence intensity is greatly enhanced by the coordination of (ZnII) with Schiff base ligands. ► The supramolecular interactions increase the conformational rigidity of chromophore groups and thus the emission intensity is much stonger.
Keywords: Schiff base ligand; Zinc(II) complex; Crystal structure; Fluorescence;

A chiral tetranuclear copper(II) complex based on a new Schiff-base ligand: Synthesis, structure, magnetic property and CD spectra by Hua Xiang; Yanhua Lan; Long Jiang; Wei-Xiong Zhang; Christopher E. Anson; Tong-Bu Lu; Annie K. Powell (51-54).
New chiral Schiff-base ligand l-H2vap, derived from the condensation of o-vanillin and l-2-amino-3-phenyl-1-propanol, reacts with Cu(Ac)2·H2O and Gd(NO3)3·6H2O in the presence of triethylamine to produce a chiral tetranuclear complex l-[Cu4(Hvap)2(vap)2(MeOH)2](NO3)2·MeOH (1). The single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in the chiral monoclinic space group P21 with Z  = 2. Four copper(II) atoms are held together by two alkoxide μ 3-O2 − atoms and two phenoxide μ 2-O2 − atoms from four individual ligands to form a boat-shaped {Cu4O4} unit. The solid-state CD spectra confirm the chiral nature of complex 1. Magnetic studies indicate that there are strong antiferromagnetic interactions between the adjacent copper(II) ions in complex 1.A chiral tetranuclear complex, l-[Cu4(Hvap)2(vap)2(MeOH)2](NO3)2·MeOH (1), has been synthesized and structurally characterized. The solid-state CD spectra and magnetic property of complex 1 were also investigated.Display Omitted► A new chiral Schiff-base ligand l-H2vap was reported. ► The synthesis, structure and CD spectra of a tetranuclear complex were investigated. ► The magnetic studies reveal strong antiferromagnetic interactions between copper(II) ions.
Keywords: Copper(II); Tetranuclear complex; Chiral; Schiff-base ligand; CD spectra; Magnetic property;

Two new coordination complexes, {[Co3(nip)2(ina)2(H2O)2]·4H2O}n (1) and {[Mn3(nip)2(ina)2]}n (2) (nip = 5-nitroisophthalic acid, ina = isonicotinic acid), have been hydrothermally synthesized from mixed rigid ligands. Complex 1 consists of linear trimeric Co3 units which are connected through double bridges into a two-dimensional (2D) (4,4) sql net. While for complex 2, the metal Mn centers are connected into infinite {⋯Mn2⋯Mn2⋯Mn1⋯}n chains which are bridged by nip and ina ligands into a 3D structure with pcu topology. Magnetic properties of the two complexes have also been studied, complex 1 displays ferromagnetic interaction between intracluster Co(II) ions, and complex 2 shows antiferromagnetic behavior.Syntheses and characterizations of two novel complexes based on mixed rigid ligands are described. Complexes 1 and 2 display 2D (4, 4) sql network and 3D pcu network, respectively. Their magnetic properties have also been investigated.Display Omitted►Two complexes based on mixed rigid ligands have been synthesized and characterized. ►Complex 1 consists of linear Co3 units and displays ferromagnetic behavior. ►Complex 2 consists of infinite metal chains and displays antiferromagnetic behavior.
Keywords: Mixed ligands; sql net; pcu net; Magnetic property;

Two {Mo36}-containing polymolybdates: Synthesis, crystal structures, and spectral characterizations by Zhangang Han; Wenbo Pei; Jingli Xie; Yang Zou; Xiao-Ming Ren (61-64).
Two polyanion clusters [Mo36O108(NO)4(H2O)16]12 − (1) and [Mo36O112(H2O)16Cu0.5(H2O)2]7 − (2) were obtained through ‘one-pot’ reaction at ambient temperature and pressure. Both of 1 and 2 consist of {Mo36} anionic clusters. Interestingly, compound 2 represents a case that the transitional metal copper is anchored into the framework of a giant {Mo36} isopolyanion.Display Omitted► Two polyanion clusters based on {Mo36} isopolyanion. ► Copper is anchored into the framework of a giant {Mo36} isopolyanion. ► Cluster anions are linked to three-dimensional structures by K+ and water molecules.
Keywords: Polyoxometalate; High-core cluster; Coordination geometry; Copper;

Guest exchange dynamics in a flexible bilayer porous coordination polymer by Shuyun Wang; Jingxin Ma; Lina Li; Tianliang Chen; Zhihua Sun; Junhua Luo (65-69).
A novel Cd(II)-organic framework [Cd(bpdc)(bpy)⋅DMF] (1) (H2bpdc = biphenyl-3,4′-dicarboxylic acid, bpy = 4,4′-bipyridine) has been synthesized by the solvothermal reaction of Cd2 + salt with H2bpdc and bpy in N,N-Dimethylformamide (DMF) solvent. Single crystal X-ray diffraction revealed that 1 has a two-dimensional (2D) bilayer structure, and the bilayers of 1 are further mutually interdigitated to form a 3D microporous framework. Guest exchange experiments for 1 with several organic solvents and water were performed, and the results display that ethanol can exchange with the guest DMF molecules in 1, but methanol, acetonitrile and water solvents can only induce 1 to extract its guest DMF molecules. Powder X-ray diffraction shows that 1 undergoes a small framework slip between the adjacent interdigitated bilayers triggered by the guest exchange, and the original framework can be restored after the exchanged samples soaked back in the DMF solvent, which demonstrated that 1 has dynamic and flexible interdigitated bilayer motif. The photoluminescent characterization shows that 1 displays blue-green emission in the solid state at room temperature.A novel two-dimensional (2D) interdigitated bilayer framework [Cd(bpdc)(bpy)⋅DMF] (1) (H2bpdc = biphenyl-3,4′-dicarboxylic acid, bpy = 4,4′-bipyridine) was synthesized by the solvothermal reaction in N,N-Dimethylformamide (DMF) solvent. Guest exchange experiments of 1 with several organic solvents and water were performed, which demonstrated the dynamic and flexibility of the interdigitated bilayer motif of 1.Display Omitted► A novel MOF (1) based on biphenyl-3,4′-dicarboxylic acid is firstly reported. ► The structure shows an interesting flexible interdigitated 2D bilayer framework. ► 1 displays interesting dynamic guest exchange properties.
Keywords: Coordination polymer; Interdigitated framework; Bilayer; Guest exchange; Flexibility; Fluorescence;

Solvothermal reaction of Ln(NO3)3·6H2O (M = Eu, Tb) with a rigid tetracarboxylate organic ligand, 5,5′-(1,2-ethynediyl)bis(1,3-benzenedicarboxylic acid) (H4EBDC), affords two novel isostructural lanthanide-based metal–organic frameworks (MOFs): [Ln(HEBDC)(DMA)(H2O)2] (Ln = Eu (1) and Tb (2), DMA = N,N′-dimethylacetamide). X-ray single-crystal structural analyses reveal that both compounds crystallize in the triclinic space group P-1. The crystal structures constructed from HEBDC3 − ligand and the binuclear Ln2 building unit. Each of the noncentrosymmetric Ln atoms is bridged through carboxyl groups to generate binuclear Ln building unit, then the binuclear building units are linked together by the organic ligands to give rise to a binodal (3,6)-connected network with a rare kgd topology. The layers further extend into 3D supramolecular frameworks via aromatic π–π stacking interactions. The compounds discussed herein exhibit strong fluorescence in the visible region at room temperature and promising luminescent properties.Two novel lanthanide MOFs [Ln(HEBDC)(DMA)(H2O)2] (Ln = Eu (1) and Tb (2)), featuring unusual binodal (3, 6)-connected kgd topology, have been synthesized. Compounds 1 and 2 exhibit strong fluorescence in the visible region at room temperature.Display Omitted► Two novel lanthanide MOFs based on rigid tetracarboxylate ligand have been synthesized. ► (3, 6)-connected network with kgd topology. ► The compounds exhibit luminescence emission.
Keywords: Lanthanide metal–organic frameworks; Tetracarboxylate ligand; kgd topology; Luminescence;

The tetranuclear cubane-like complex of the formula [Ni4(HL1)3(HL2)(H2O)(CH3OH)] [CH3COO]·2CH3OH·CH3CN (1) (H3L1 = 3-(2-hydroxybenzylideneamino)propane-1,2-diol; H2L2 = 3-aminoprppane-1,2-diol) has been prepared by a one-pot reaction of nickel(II) acetate, salicylaldehyde and 3-aminopropane-1,2-diol, where the H3L1 ligand was generated in situ via the condensation reaction between salicylaldehyde and 3-aminopropane-1,2-diol. The X-ray diffraction analysis of the complex showed a Ni4O4 cubane arrangement and the coordination environments of four Ni(II) ions are different from each other. Magnetic studies indicated ferromagnetic behavior for the complex. The magnetic data were fitted and the parameters were given as g  = 2.43, J 1  = 15.96, and J 2  = 4.116.The tetranuclear cubane-like complex of the formula [Ni4(HL1)3(HL2)(H2O)(CH3OH)] [CH3COO]·2CH3OH·CH3CN (1) has been prepared and structurally characterized. Magnetic studies indicate ferromagnetic behavior for the complex.Display Omitted►A tetranuclear Ni4O4 cubane-like complex has been prepared and characterized. ►The coordination environments of four Ni(II) ions are different from each other. ►Magnetic studies indicate ferromagnetic behavior for the complex.
Keywords: Tetranuclear; Cubane-like; Nickel complex; Magnetic properties;

Synthesis and characterization of CoIII 3 inverse metallacrowns via use of 6-methyl-2-pyridylaldoxime by Gina Vlahopoulou; Albert Escuer; Mercè Font-Bardia; Teresa Calvet (78-80).
The use of 6-methyl-2-pyridylaldoxime (6-mepaoH) in cobalt carboxylate chemistry has yielded metallacrowns with general formula [CoIII 3(μ 3-O)(O2CMe)3(6-mepao)3]2[CoII(L)4] (1⋅ 2MeOH ⋅ 1.5H2O, L  = AcO and 2⋅ 2.5H2O, L  = NCS). Compounds 1 and 2 display an unusual structural motif in cobalt-oximate chemistry, consisting of CoIII triangles centered by one μ 3-oxo ligand. Crystal structure and EPR characterization of CoII anions are reported.The use of 6-methyl-2-pyridylaldoxime (6-mepaoH) in reactions with CoII acetate has yielded compounds [CoIII 3O(O2CMe)3(6-mepao)3]2[CoII(O2CMe)4]⋅ 2MeOH ⋅ 1.5H2O (1⋅ 2MeOH ⋅ 1.5H2O) and [CoIII 3O(O2CMe)3(6-mepao)3]2[CoII(NCS)4]⋅ 2.5H2O (2⋅ 2.5H2O). The [CoIII 3] units of compounds 1 and 2 could alternatively be described as chiral inverse 9-metallacrown-3 complexes.Display Omitted► Pyridyl oximate ligands generate inverse metallacrowns. ► Cobalt oxo-centered triangles can be generated with oximes. ► Anions plays a crucial role in the stabilization of cobalt triangles.
Keywords: Cobalt complexes; Metallacrowns; Oxo-centered complexes; 6-Methyl-2-pyridylaldoxime; EPR spectra;

In order to conduct photoactive catalysts for hydrogen production, a novel trimetallic [Re-Fe] complex 1, consisting of the phenanthroline rhenium photosensitizer and the [2Fe2S] complex (connected by the axial coordination of a pyridyl group), was prepared and spectroscopically characterized. The apparent fluorescence quenching of the complex 1 was observed in comparison with the reference complex 1b, suggesting the possibility for an electron transfer from the excited state of the rhenium moiety to the [2Fe2S] moiety. Visible light-driven H2 generation was achieved by using triethylamine (sacrificial electron donor) in the presence of the complex 1 (catalyst) in CH3CN/H2O, with a turnover number reaching to 1.5. This is by far as we know the highest for the [Re-Fe] photocatalysts. In contrast to the molecular device, the multicomponent catalyst of complexes 1b and 1c, no H2 was detected by GC analysis in the same experimental condition. The plausible mechanism for the photochemical H2-evolution with this molecular device is discussed.A novel trimetallic [Re–Fe] complex 1 was prepared and spectroscopically characterized. Visible light-driven H2 generation was achieved by using triethylamine in the presence of complex 1 in CH3CN/H2O, with a turnover number reaching to 1.5, so far as we know the highest for the [Re–Fe] photocatalysts.Display Omitted► A novel [Re–Fe] photocatalyst and its reference complexes were synthesized and characterized. ► Fluorescence quenching suggested a possibility for an electron transfer from the rhenium moiety to the [2Fe2S] moiety. ► The [Re–Fe] photocatalyst can catalyze the hydrogen evolution with the TEA as the electron donor. ► Its turnover number reach to 1.5, so far the highest for the [Re–Fe] photocatalysts.
Keywords: Rhenium; Hydrogen evolution; Photocatalysis; [2Fe2S] complex;

A new homochiral metal-organic framework [ZnMg(btc)(H2O)4](NO3) (1, btc = 1,3,5-benzenetricarboxylate) with unusual 3-connected heterometallic ZnMg(COO)3 building blocks has been solvothermally synthesized and structurally characterized with the aid of single crystal X-ray diffraction. Compound 1 crystallizes in a chiral space group and exhibits 3-connected srs structural topology. The results reveal the first srs-type metal-organic framework constructed from heterometallic building blocks.Presented here is a new homochiral srs-type zinc-organic framework with unusual 3-connected heterometallic ZnMg(COO)3 building blocks.Display Omitted► A new homochiral zinc-organic framework with unusual 3-connected heterometallic ZnMg(COO)3 building blocks ► The 3-connected srs structural topology observed in a heterometallic coordination polymer ► Interesting helical structure assembled from Zn(II) ions and 1,3,5-benzenetricarboxylate ligands.
Keywords: Metal-organic framework; Zinc; Topology; Chiral; Crystal structure;

Ferroelectric and mesomorphic properties of oxovanadium(IV) complexes with long alkoxy chains by Asuka Ohta; Yuuki Yamamoto; Hidenobu Kamihata; Young Hoon Lee; Fusao Ichikawa; Kazuchika Ohta; Yuriko Abe; Naomi Hoshino; Masaaki Kojima; Shinya Hayami (89-91).
The chiral and racemic oxovanadium(IV) salmmen complexes, [VO(X)-(C16-salmmen)] (X  =  R(1), S(2), and rac(3); C16-salmmen =  N,N′-monomethylenebis(5-hexadecyloxysalicylideneimine)) containing 5-substituted alkoxy chains on aromatic rings were synthesized, and their mesomorphic behaviors and ferroelectric properties were also investigated. All complexes exhibited both smectic A and chiral smectic C mesophases above 360 K, and they showed ferroelectric properties in the chiral smectic C mesophase.The chiral and racemic oxovanadium(IV) salmmen complexes [VO(X)-C16-salmmen)] (X  =  R, S and rac) were synthesized. All complexes exhibited both smectic A and chiral smectic C mesophases above 360 K, and ferroelectric property was observed even for racemic compound.Display Omitted► The chiral and racemic oxovanadium(IV) salmmen complexes were synthesized. ► All complexes exhibited both smectic A and chiral smectic C mesophases above 360 K. ► They showed ferroelectric properties in the chiral smectic C mesophase.
Keywords: Metallomesogen; Ferroelectricity; Liquid crystal; Oxovanadium(IV) complex;

Two novel 2D metal–organic frameworks based on biphenyl-2,2′,6,6′-tetracarboxylic acid: Synthesis, structures and luminescent properties by Zhi Yang; Jia Liu; Xiao-Qiang Liang; Yuan Jiang; Ting Zhang; Bing Han; Fu-Xing Sun; Lei Liu (92-94).
Two novel metal–organic frameworks (MOFs) assembled from H4BPTC, {[Co2(BPTC)(H2O)4(DMF)2]2H2O} 1, {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2, (H4BPTC = biphenyl-2,2′,6,6′-tetracarboxylic acid, DMF = N,N-dimethylformamide) have been obtained under hydrothermal conditions, and structurally characterized by single-crystal X-ray diffraction. The results reveal that compounds 1 and 2 are isostructural except the different metal centers, exhibiting a 2D layer structure with 4–4 net. 1 and 2 are also characterized by elemental analysis, IR spectra, TGA analysis and PXRD. The luminescent properties of 1 and 2 in solid state are discussed.Two novel 2D metal–organic frameworks (MOFs) based on H4BPTC, {[Co2(BPTC)(H2O)4(DMF)2]2H2O}1, {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2, (H4BPTC = biphenyl-2,2,6′,6′-tetracarboxylic acid, DMF = N,N′-dimethylformamide) have been obtained under hydrothermal conditions, and well characterized by single-crystal X-ray diffraction,elemental analysis, IR spectra, TGA analysis, PXRD and luminescent spectra. The results reveal that these two compounds are isostructural except the different metal centres, exhibiting a 2D layer structure with 4-4 net.Display Omitted► We obtained two novel MOFs from a kind of tetracarboxylic acid ligand. ► These two compounds are isostructural exhibiting layers with 4-4 net. ► Luminescence of compounds in solid state are blue-shifted from free ligand.
Keywords: Biphenyl-2,2′,6,6′-tetracarboxylic acid; Luminescent properties;

Two novel 3D microporous heterometallic 3d–4f coordination frameworks with unique (7, 8)-connected topology: Synthesis, crystal structure and magnetic properties by Xia Zhao; Xiao-Ping Ye; Li-Mei Chang; Zhi-Qiang Wei; Wen-Jing Liu; Shan-Tang Yue; Ying-Liang Liu; Hai-Hong Mo; Yue-Peng Cai (95-99).
Two new 3D 3d–4f heterometallic microporous metal-organic frameworks, named, [Ln2Ni(Himdc)2(aip)2(H2O)4]·6H2O [Ln = Nd (1), La (2); H3imdc = imidazole-4,5-dicarboxy acid; aip = 5-aminoisophthalic acid], have been successfully synthesized through the reaction of Ln2O3, NiSO4·6H2O, H3imdc, aip and H2O. Compounds 1 and 2 are isomorphic, displaying rare interesting 3D heterometallic networks with (7, 8)-connected topology based on the linkages of 2D layers and 1D zigzag chains. In addition, the magnetic properties of the two compounds have been investigated.The 2D layer structure based on 1D zigzag chains and Ni(II) centers, and further linked by the aip ligands to form interesting 3D microporous frameworks.Display Omitted► Two novel 3D heterometallic microporous complexes have been synthesized. ► The 3D heterometallic network with (7, 8)-connected topology. ► Both complexes exhibit antiferromagnetic behavior.
Keywords: Hydrothermal synthesis; Heterometallic; Microporous; Magnetism;

Three novel two–dimensional (2–D) coordination polymers {[Ln (bpdc) (BDC)0.5 (DMF) (H2O)]·1.5H2O} n [Ln = Tb (1), Sm (2), Gd (3); H2bpdc = 2,4′–biphenyldicarboxylic acid; H2BDC = 1,4–benzenedicarboxylic acid, and DMF =  N,N′–dimethylformamide] have been successfully synthesized by the reactions of metal source Ln(NO3)2·5H2O with mixed aromatic carboxylate ligands named, H2bpdc and H2BDC in the mixed solution of DMF and H2O. Complexes 13 were characterized by element analyses, IR spectroscopy and single–crystal X–ray diffraction. The results reveal that three complexes are isostructural. In the molecular structure of 1, the neighboring Tb3+ cations are connected by the edge sharing fashion from two three-bridging μ 3 –oxygen atoms to construct a dinuclear polyhedron. The adjacent dinuclear units are linked by two bpdc2– ligands to form an infinite double zigzag chain containing quadrangular grids. These chains are linked by BDC2–, which acted as pillar to form a 2-D layered structure containing (4, 4) networks. The solid–state luminescent properties of complexes 1 and 2 were investigated at room temperature. Complexes 1 and 2 have displayed their characteristic emissions and decay lifetimes.Three novel two-dimensional (2-D) coordination polymers {[Ln (bpdc) (BDC)0.5 (DMF) (H2O)]·1.5H2O} n [Ln = Tb (1), Sm (2), Gd (3); H2bpdc = 2,4′–biphenyldicarboxylic acid; H2BDC = 1,4–benzenedicarboxylic acid, and DMF =  N,N′–dimethylformamide] have been successfully synthesized by the reaction of metal source Ln(NO3)2·5H2O with mixed aromatic carboxylate ligands named, H2bpdc and H2BDC in the mixed solution of DMF and H2O. Complexes 13 were characterized by element analysis, IR spectroscopy and single–crystal X–ray diffraction. The solid–state luminescent properties of complexes 1 and 2 were investigated at room temperature. Complexes 1 and 2 have displayed their characteristic emissions and decay lifetimes.Display Omitted►Three novel 2-D coordination polymers with mixed aromatic carboxylate ligands. ►This is the first example of the Ln–MOFs containing both H2bpdc and H2DBC ligands. ►Complexes 1 and 2 have displayed the characteristic emissions and decay lifetimes.
Keywords: 2-D coordination polymers; Mixed aromatic carboxylate ligands; Dinuclear polyhedron; Luminescent properties;

[Ru(bpy)2(pipdpa)]2+ as a highly sensitive and selective luminescent chemosensor for Cu2+ in aqueous solution by Qi-Tian Lin; Ling-Min Pei; Wen-Chao Xu; Hui Chao; Liang-Nian Ji (104-106).
A novel ruthenium(II) polypyridyl complex [Ru(bpy)2(pipdpa)]2+ (1) with DPA (dipicolylamine) moiety as receptor (bpy = 2,2′-bipyridine, pipdpa=2-(4′-N,N-bis(pyridin-2-ylmethyl)aniline)imidazo[4,5-f][1,10]phenanthroline) was developed as a luminescent chemosensor with high selectivity and antidisturbance toward Cu2+ over other tested metal ions (Ca2+, Cd2+, Co2+, Hg2+, K+, Mg2+, Mn2+, Na+, Ni2+, Pb2+, Zn2+, Fe2+, Fe3+). Remarkably, complex 1 could be applied to detect Cu2+ with a wide pH range 3–10 in aqueous solution.A novel ruthenium(II) polypyridyl complex [Ru(bpy)2(pipdpa)]2+ (1) was developed as a highly sensitive and selective luminescent chemosensor for Cu2+ in aqueous solution.Display Omitted► [Ru(bpy)2(pipdpa)]2+ (1) was developed as a luminescent chemosensor for Cu2+. ► Complex 1 showed high sensitivity and selectivity toward Cu2+. ► Complex 1 displayed well solubility in aqueous solution. ► Complex 1 could be applied to detect Cu2+ with a wide pH range 3–10.
Keywords: Ruthenium(II) polypyridyl complex; DPA moiety; Luminescent chemosensor; Cu2+;