Inorganic Chemistry Communications (v.14, #3)

Contents List (iii-vii).

Reported here is an anionic framework material [(CH3)2NH2]2[Cd3(BPTC)2]. (DMF) (1), which features a pillared-layer structure with 1D channels occupied by the guest [(CH3)2NH2]+ cations. The physical properties such as thermogravimetric analyses (TGA), powder X-ray diffraction (PXRD), and gas adsorption were investigated. Additionally, we find that compound 1 may act as a good luminescent sensor to detect the Tb3+ ion.An anionic framework material [(CH3)2NH2]2[Cd3(BPTC)2].(DMF) (1) with pillared-layer structure, showing 1D channels occupied by the guest [(CH3)2NH2]+ cations, was solvothermally synthesized and structurally characterized.Display Omitted► A new microporous metal-3,3′4,4′-benzophenone-tetracarboxylate framework material with 1D open-channels. ► An organically templated 3D anionic framework. ► A microporous material with selective CO2 uptake.
Keywords: Metal-organic framework; 3,3′4,4′-benzophenone-tetracarboxylate; Solvothermal synthesis; Porous material;

A porous indium(III) metal-organic framework, [In2(OH)2(C10O8H2)]n·2nH2O (MIL-60), has been synthesized by hydrothermal method and characterized by elemental analyses, X-ray powder diffraction (XRD) and IR spectroscopy. Indium(III) oxide nanoparticles have been prepared by direct thermal decomposition of compound MIL-60 at 450 °C under air atmosphere. The indium(III) oxide nanoparticles were characterized by scanning electron microscopy, X-ray powder diffraction (XRD). This study demonstrates that the porous metal-organic framework may be suitable precursors for the simple one-pot preparation of nanoscale metal oxide materials with different and interesting morphologies.A porous indium(III) metal-organic framework, [In2(OH)2(C10O8H2)]n·2nH2O (MIL-60), has been synthesized by hydrothermal method and characterized by elemental analyses, X-ray powder diffraction (XRD) and IR spectroscopy. Indium(III) oxide nanoparticles have been prepared by direct thermal decomposition of compound MIL-60 at 450 °C under air atmosphere. The indium(III) oxide nanoparticles were characterized by scanning electron microscopy, X-ray powder diffraction (XRD).Display Omitted► A porous In(III) metal-organic framework as precursor. ► Synthesis of In2O3 nano –particles from one porous coordination polymer precursor. ► In2O3 nano –particles with uniform shape and good size distribution.
Keywords: Metal-Organic Framework; Indium(III) oxide; Nano-material; Porous; Calcination;

2D pillar-chained 3d-4f heterometallic coordination polymers based on 2,4′-biphenyldicarboxylate by Xiao-Yi Yi; Yin Ying; Hua-Cai Fang; Zhi-Gang Gu; Sheng-Run Zheng; Qing-Guang Zhan; La-Sheng Jiang; Wei-Shan Li; Feng-Qiang Sun; Yue-Peng Cai (453-457).
Two new 2D 3d-4f heterometallic compounds [LnIIICuII(2,4′-bpdc)2(μ 3-OH)(C2H5OH)H2O]n (Ln = Tb(1) and Eu(2), 2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) have been successfully constructed by the solvothermal reaction of Ln2O3, Cu(NO3)2 and 2,4′-H2bpdc in ethanol, and characterized by element analysis, IR spectroscopy, and thermal analysis, as well as single crystal X-ray diffraction. The results reveal that two complexes are isomorphous and exhibit 2D pillar-chained coordination frameworks with 36·46·53 topology constructed from one-dimensional lanthanide-transition oxo-bridged heterometallic chains [LnCu(μ 2-O)2(μ 3-OH)2]n and (2,4′-bpdc2−)2 pillars. Furthermore, the photoluminescent properties of two compounds 1 and 2 were also studied.Two new 3d-4f heteronuclear 2D frameworks with 36·46·53 topology constructed from one-dimensional lanthanide-transition oxo-bridged heterometallic chains [LnCu(μ 2-O)2(μ 3-OH)2]n and (2,4′-bpdc2−)2 pillars, which denotes the first example of 3d-4f complexes including alone 2,4′-biphenyldicarboxylic acid.Display Omitted► Two new 3d-4f heteronuclear 2D frameworks with 36·46·53 topology. ► Constructed from 1D chains [LnCu(μ2-O)2(μ 3-OH)2]n and (2,4′-bpdc2-)2 pillars. ► Denotes the first example of 3d-4f complexes including alone 2,4′- biphenyldicarboxylate.
Keywords: 2D 3d-4f heterometallic ploymers; 2,4′-Biphenyldicarboxylate; Oxo-bridged heterometallic chain; Fluorescence;

Construction of one 2D samarium-organic framework based on 2,4′-biphenyldicarboxylate by Xiao-Yi Yi; Zhi-Gang Gu; Ming-Fang Wang; Hong-Yang Jia; Hui-Min Peng; Yin Ying; Xue Gong; Wei-Shan Li; Feng-Qiang Sun; Yue-Peng Cai (458-462).
A new 2D samarium compound [Sm(2,4′-bpdc)(2,4′-Hbpdc)H2O]n (1) (2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) has been successfully constructed by the hydrothermal reaction of Sm2O3 with 2,4′-H2bpdc, and characterized by elemental analysis, IR spectroscopy and thermogravimetric analysis, as well as single-crystal X-ray diffraction. The results reveal that complex 1 possesses a 2D framework with 44 topology constructed from one-dimensional lanthanide-carboxylate meso-helical chains [Sm(O–C–O)2]n ( Δ  +  Λ ) and (2,4′-bpdc2−)2 pillars; this complex represents the first example of a lanthanide compound containing 2,4′-biphenyldicarboxylate as the sole ligand. Moreover, compound 1 displays a certain photoluminescent property and high thermal stability.One new 2D framework with 44 topology constructed from one-dimensional lanthanide-carboxylate meso-helical chains [Sm(O–C–O)2]n ( Δ  +  Λ ) and (2,4′-bpdc2−)2 pillars, which represents the first example of a lanthanide complex possessing the ligand 2,4′-biphenylcarboxylate with different coordination modes.Display Omitted► A number of lanthanide metal–organic frameworks (LMOFs) with fascinating architecture have been synthesized via dicarboxylate ligands. ► However, few effort has been devoted to the investigation of transition/lanthanide-metal coordination chemistry involving 2,4′-biphenyldicarboxylic acid up to now. ► To the best of our knowledge, the compound [Sm(2,4′-bpdc)(2,4′-Hbpdc)H2O]n (1) (2,4′-H2bpdc = 2,4′-biphenyldicarboxylic acid) reported in the manuscript is the first example of the lanthanide coordination polymer containing single 2,4′-H2bpdc ligand.
Keywords: 2D samarium-organic framework; 2,4′-biphenyldicarboxylate; Meso-helix; Fluorescence;

A novel coumarin Schiff-base as a Zn(II) ion fluorescent sensor by Mi-hui Yan; Tian-rong Li; Zheng-yin Yang (463-465).
A new fluorescent Zn2+ chemosensor, 8-(7′-Hydroxy-4′-methylcoumarin-8′-yl-) methyleneiminoquinoline (L) was designed and synthesized. This complex could act as highly sensitive and selective fluorescent probe for Zn2+ in THF (tetrahydrofuran). However, other metal ions gave little fluorescence change.A new fluorescent Zn2+ chemosensor, 8-(7′-Hydroxy-4′-methylcoumarin-8′-yl-) methyleneiminoquinoline (L) was designed and synthesized. This complex could act as highly sensitive and selective fluorescent probe for Zn2+ in THF.Display Omitted► A novel coumarin Schiff-base is synthesized. ► The compound exhibits higher selectivity and sensitivity for Zn2+ than other metal ions. ► The Schiff-base ligand can be synthesized easily.
Keywords: Zinc chemosensor; Fluorescence; Coumarin; 8-Aminoquinoline;

Structural peculiarities of actinyl complexation with monolacunary polyoxometalates by Marina N. Sokolova; Grigory B. Andreev; Aleksander B. Yusov (466-469).
Uranium(VI) complex with silicoundecatungstate, K7H6[K(UO2)(H2O)(α-SiW11O39)2]·21H2O, has been obtained and its structure has been determined using X-ray single crystal diffractometry and confirmed by electron and IR absorption spectroscopy. The stability of An(VI) complexes with monolacunary heteropolyanions in solution is discussed from the structural point of view.Crystal structure of uranium(VI) complex with silicoundecatungstate, K7H6[K(UO2)(H2O)(α-SiW11O39)2]·21H2O, has been determined using X-ray diffractometry and confirmed by electron and IR absorption spectroscopy. The stability of An(VI) complexes with monolacunary heteropolyanions in solution is discussed from the structural point of view.Display Omitted► Crystal structure of K7H6[K(UO2)(H2O)(α-SiW11O39)2]·21H2O has been determined. ► The uranium atom coordinates two oxygen atoms of lacuna of each anion. ► The pH-dependence of An(VI) complexes stability is explained.
Keywords: Actinides; Polyoxometalates; Crystal structure; X-ray diffraction; Spectroscopy;

Reaction of bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) with [MoCl4(Ac)2], in acetonitrile (Ac) at room temperature results in obtaining [Mo(IV)Cl3(bdmpza)]∙Ac (1) (Ac = acetonitrile). The treatment of 1 in pyridine (py) gives pyH[Mo(III)Cl3(bdmpza)]∙2py (2) (py = pyridine. The complexes were characterized by X-ray structure analysis, UV-visible and IR spectroscopy. The coordination spheres in the molecule [MoCl3(bdmpza)] and in the anion [MoCl3(bdmpza)] are the same. Both species exhibit a six-coordinate distorted octahedral geometry. They differ only in the oxidation state of the central molybdenum ion.Two novel mononuclear neutral octahedral Mo(IV) and Mo(III) complexes have been prepared. The reaction of [MoCl4(CH3CN)2] with tripod heteroscorpionate N,N,O-ligand (Hbdmpza) results in [MoIVCl3(bdmpza)] (1). By reduction with pyridine 1 changes into [MoIIICl3(bdmpza)] (2).Display Omitted► Synthesis of Mo(IV) and Mo(III) complexes with N,N,O-scorpionate ligand Hbdmpza. ► Complexes: [MoCl3(bdmpza)] ∙ CH3CN and pyH[MoCl3(bdmpza)]∙2py. ► X-ray crystal structure analysis, IR and UV-Vis spectra of complexes
Keywords: Scorpionate ligands; Hbdmpza; Molybdenum(IV); Molybdenum(III); X-ray structure;

A new 2D network polyoxometalate constructed from Strandberg-type phosphomolybdates linked through binuclear Ca(II) clusters by Jingyang Niu; Junchuang Ma; Junwei Zhao; Pengtao Ma; Jingping Wang (474-477).
A polyoxometalate cluster based on Strandberg-type phosphomolybdate [K3Ca(H2O)4(HP2Mo5O23)]·6H2O (1) has been synthesized by the conventional solution method and characterized by IR spectrum, UV spectra, electrochemical measurements, thermogravimetric analysis, ICP techniques and X-ray crystallography. X-ray single crystal diffraction analysis shows that 1 contains a novel polyoxoanion [Ca(H2O)4(HP2Mo5O23)]3− (1a) based on a Strandberg-type phosphomolybdate [HP2Mo5O23]5−. Notably, it represents the first 2D polymolybdate inorganic structure constructed from Strandberg-type phosphomolybdates linked through alkaline earth metal clusters. Interestingly, the phenomenon that 1a and heteropolyoxoanion {[Ca(H2O)]6[P4Mo6O34]2}12− can be mutually transformed when the pH of the solution is adjusted to ca. 4.50 in aqueous solution has been observed.A polyoxometalate cluster based on Strandberg-type phosphomolybdate [K3Ca(H2O)4(HP2Mo5O23)]·6H2O has been synthesized by the conventional solution method and characterized by IR spectra, UV spectra, electrochemical measurements, TG analyses and X-ray crystallography. The interesting phenomenon that 1a and heteropolyoxoanion {[Ca(H2O)]6[P4Mo6O34]2}12− can be mutually transformed when the pH of the solution is adjusted to ca. 4.50 in aqueous solution has been observed.Display Omitted► A polyoxometalate cluster based on Strandberg-type phosphomolybdate [K3Ca(H2O)4(HP2Mo5O23)]·6H2O has been synthesized by the conventional solution method and characterized by IR spectra, UV spectra, electrochemical measurements, TG analyse and X-ray crystallography. ► The polyoxometalate represents the first inorganic 2D layer Strandberg-type phosphomolybdate. ► The polyoxometalate enriches the structural diversity of Strandberg-type polyoxometalates. ► The heteropolyoxoanions [Ca(H2O)4(HP2Mo5O23)]3– and {[Ca(H2O)]6[P4Mo6O34]2}12– can be mutually transformed when the pH of solution is adjusted to ca. 4.50 in aqueous solution.
Keywords: Polyoxometalate; Alkaline earth metal; Strandberg; Inorganic cluster;

A facile one-step access to a chiral at metal ruthenium phosphoramidite tri(N-pyrrolyl)phosphine (PPyrl3) complex is reported. In a one-pot reaction with PPyrl3 and a chiral phosphoramidite ligand (L), the known ruthenium indenyl complex [RuCl(Ind)(PPh3)2] (Ind = indenyl) was converted to the chiral at metal complex [RuCl(Ind)PPyrl3(L)] as an optically pure single diastereomer in 59% isolated yield. The new complex was characterized spectroscopically and by X-ray crystallography, revealing a profound impact of the PPyrl3 ligand on the geometry of the novel ruthenium complex.Display Omitted►Synthesis of the first chiral at metal tri(N-pyrrolyl)phosphine complex ►Easy access to the title compound in a one-pot procedure ►Profound impact of the tri(N-pyrrolyl)phosphine on the structure of the complex
Keywords: Chiral at metal; Pyrrolyl phosphine ligand; Phosphoramidite ligand; X-ray; One-pot procedure;

Preparation of cisplatin using microwave heating and continuous-flow processing as tools by Elizabeth A. Pedrick; Nicholas E. Leadbeater (481-483).
Microwave heating has been used for the small-scale preparation of cisplatin, [cis-PtCl2(NH3)2], in isomerically pure form without concomitant formation of Magnus’ salt, [Pt(NH3)4][PtCl4]. In scaling up the reaction to the gram level, continuous-flow processing was employed.Microwave heating is used for fast, easy preparation of cisplatin. For scale up, continuous‐flow processing is employed.Display Omitted►Microwave heating used for the small‐scale synthesis of cis‐platin, [cis‐PtCl2(NH3)2]. ►Continuous‐flow processing used for scale‐up. ►Product is isomerically pure. ►Product is formed in short reaction times. ►No formation of Magnus’ salt [Pt(NH3)4][PtCl4] when using optimized conditions.
Keywords: Cisplatin; Cancer; Microwave heating; Flow chemistry; Platinum chemistry; Water;

A series of lanthanide coordination polymers with 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine: Syntheses, crystal structures and luminescence properties by Qing-Ran Wu; Ji-Jiang Wang; Huai-Ming Hu; Yi-Qing Shangguan; Feng Fu; Meng-Lin Yang; Fa-Xin Dong; Gang-Lin Xue (484-488).
A series of lanthanide coordination polymers, [Ln(cptpy)3] n [Ln = Sm (1), Eu (2), Tb (3), Dy (4), Hcptpy = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine] have been prepared under hydrothermal conditions and characterized by IR, Elemental analysis, single crystal X-ray diffraction. Compounds 14 are isostructural with 1D framework, in which all LnIII atoms are nine-coordinated and (cptpy) anions adopt two different coordination modes. The network packed through π···π stacking interactions and C–H···π interactions to form a 3D supramolecular structure without solvent molecules. In addition, the thermal stabilities and luminescence properties were also studied.A series of lanthanide coordination polymers, [Ln(cptpy)3] n [Ln = Sm (1), Eu (2), Tb (3), Dy (4), Hcptpy = 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine] have been prepared under hydrothermal conditions and characterized. Their photoluminescence properties were also studied. The thermal stabilities and lifetime of 2 were further studied.Display Omitted► A series of lanthanide coordination polymers, [Ln(cptpy)3]n have been prepared. ► The 3D supramolecular structure is formed through π···π and C–H···π interactions. ► The (cptpy)- anion can efficiently sensitize EuIII luminescence.
Keywords: Lanthanide coordination polymers; Crystal structures; 4′-(4-carboxyphenyl)-2,2′:6′,2″-terpyridine; Luminescence;

Mononuclear copper(II) complex [Cu(Pyimpy)(Cl)(ClO4)] has been synthesized from a tridentate ligand Pyimpy (Pyimpy = 1-phenyl-1-(pyridin-2-yl)-2-(pyridin-2-ylmethylene)hydrazine) and characterized by elemental analysis, electronic absorption and IR spectroscopy. Molecular structure of 1 was determined by single crystal X-ray diffraction. Structural index parameter (τ) calculation supported distorted square pyramidal geometry around the metal centre. The stabilization of copper(II) centre was examined by electrochemical studies. DNA interaction studies were investigated by absorption spectral studies and EthBr displacement assay. Nuclease activity studies afforded cleavage of pBR322 plasmid DNA via self-activating mechanism. Investigation of mechanism indicated the possible role of reactive oxygen species in DNA cleavage.Mononuclear copper(II) complex [Cu(Pyimpy)(ClO4)(Cl)] derived from tridentate ligand Pyimpy (Pyimpy = 1-phenyl-1-(pyridin-2-yl)-2-(pyridin-2-ylmethylene)hydrazine) showed formation of a new species during DNA interaction. Nuclease activity studies afforded cleavage of pBR322 plasmid DNA in absence of any oxidizing or reducing agents. Inhibition of nuclease activity was observed in presence of radical scavengers and possible role of reactive oxygen species was speculated.Display Omitted► Copper complex. ► Structure solution. ► DNA binding. ► Nuclease activity.
Keywords: Copper complex; Crystal structure; Electrochemistry; DNA binding; Nuclease activity;

Hydrothermal reaction of copper(II) salt with mixed ligands afford two new coordination polymers formulated as [Cu(mip)(bpmp)0.5]·H2O (1) and [Cu(mip)(bpe)0.5] (2) (H2mip = 5-methylisophthalic acid, bpmp =  N,N′-bis-(4-pyridyl-methyl) piperazine, bpe = 1,2-bis-(4-pyridyl) ethane). X-ray diffraction analyses show that both 1 and 2 are 3D doubly interpenetrating networks based on α-Po primitive cubic units.Two 3D doubly interpenetrating networks based on α-Po primitive cubic units assembled from mixed flexible neutral ligands and rigid charge compensated ligand systems are reported.Display Omitted► 3D doubly interpenetrating networks based on α-Po primitive cubic units. ► Interpenetrating networks assembled from mixed ligands. ► Mixed flexible neutral ligands and rigid charge compensated ligand system.
Keywords: Coordination polymer; Interpenetrating network; Copper(II) complex; Bipyridyl ligand;

Schiff base molybdenum (VI) complexes were immobilized onto a novel polymer–inorganic hybrid support-zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA). The immobilized catalysts were well characterized by IR, BET, XPS, SEM and TEM. Compared with other heterogeneous catalysts known from the relative literatures, the as-prepared heterogeneous catalysts showed comparable or even higher conversion and chemical selectivity, which was mainly attributed to the special structure and composition of ZPS-PVPA. Moreover, the supported catalysts were easily recovered by simple filtration and could be reused at least ten times with little loss of activity.Schiff base molybdenum (VI) complexes were immobilized onto a novel polymer–inorganic hybrid support-zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA). The immobilized catalysts were well characterized by IR, BET, XPS, SEM and TEM. Compared with other heterogeneous catalysts known from the relative literatures, the as-prepared heterogeneous catalysts showed comparable or even higher conversion and chemical selectivity, which was mainly attributed to the special structure and composition of ZPS-PVPA. Moreover, the supported catalysts were easily recovered by simple filtration and could be reused at least ten times with little loss of activity.Display Omitted► Polystyrene–zirconium phosphate composite material (ZPS-PVPA) has special new characteristics, such as possessing caves, holes, micropores, channels and secondary channels with various sizes and shapes. ► Immobilized Schiff base molybdenum complexes show a promising application potential for epoxidation of unfunctionalized olefins. ► Our catalysts were easily recovered by simple filtration and could be reused at least ten times with little loss of activity.
Keywords: Zirconium poly (styrene-phenylvinylphosphonate)-phosphate; Molybdenum (VI) complexes; Nanocomposite; Heterogeneous catalyst; Epoxidation;

In the past few years, CdII coordination polymers have received much attention due to their diverse structures and interesting properties. This mini-review presents a short summary of the structural styles for such metal-organic networks based on their extended dimensions. Moreover, the influence factors on assemblies and some potential applications will also be commented.The recent progress of CdII coordination polymers is briefly reviewed in the aspects of their diverse structures, adjustable assemblies, and potential applications.Display Omitted► CdII can adopt flexible coordination numbers and geometries. ► CdII coordination polymers show diverse network structures. ► Assembly of CdII coordination polymers may be sensitively influenced. ► CdII coordination polymers have potentially applications.
Keywords: CdII coordination polymers; Crystal engineering; Structural diversity; Supramolecular assemblies; Properties;