Inorganic Chemistry Communications (v.39, #C)

Contents List (iii-xii).

A novel 4-connected binodal Moganite net with three-fold interpenetration by Shu-yun Huang; Jian-qiang Li; Xiao-liu Wu; Xiao-min Zhang; Ming-biao Luo; Feng Luo (1-4).
Reported here is a novel Cd(II) coordination polymer (namely [Cd(L1)0.5(ntd)]n (1), L1 = N,N′-di(4-pyridyl)adipoamide, H2ntd2  = 1,4-naphthalenedicarboxylic acid). Single-crystal X-ray diffraction reveals that the framework can be represented as metal/organic-binodal 4-connected Moganite net with three-fold interpenetration. Importantly, for the first time, an unusual coordination mode is observed for the acylamide ligand in such manner that every L1 ligand links four Cd(II) ions through two nitrogen atoms from two pyridine groups and two oxygen atoms from two acylamide groups.Display Omitted
Keywords: Cd(II) coordination polymer; Mixed ligand; Binodal; 4-Connected net; Three-fold interpenetration; Moganite net;

Two new Ni(II) complexes, namely [NiL(bpy)0.5(H2O)2]·2H2O (1) and [NiL(bpy)0.5]n (2), respectively, were constructed from the same initial materials thiazolidine-2,4-dicarboxylic acid (H2L), 4,4′-bipyridine and NiCl2·6H2O, exhibiting varying architectures from 0D to 3D by changing reaction temperature. The transformation was confirmed by powder X-ray diffraction, infrared spectra and elemental analysis. The magnetic behaviors of 1 and 2 were investigated as well.Two new Ni(II) complexes were synthesized, which exhibited a structural transformation from 0D to 3D network through the variation of temperatures.Display Omitted
Keywords: Ni(II); Coordination polymer; Structural transformation; Magnetic property;

A new mixed metal borate LiBa1.5[B5O8(OH)3] (1) has been hydrothermally synthesized and structurally characterized by FT-IR spectroscopy, powder X-ray diffraction, single crystal X-ray diffraction, and thermogravimetric analysis, respectively. 1 crystallizes in the monoclinic system, space group C2/c, a  = 11.2839(7) Å, b  = 7.3974(4) Å, c  = 20.7151(13) Å, β  = 103.392(6)°, V  = 1682.10(17) Å3 and Z  = 8. The structure consists of infinite one-dimensional (1-D) borate chains constructed from B5O9(OH)3 6 − cluster units. These B―O chains are further linked by the Ba2 + and Li+ cations to form a 3-D framework.A new mixed metal borate, LiBa1.5 [B5O8(OH)3], has been hydrothermally made, which consists of 1-D borate chains made of B5O9(OH)3 cluster units and further linked by Ba and Li atoms to form the 3-D framework.Display Omitted
Keywords: Metal borate; Cluster; Hydrothermal synthesis; Crystal structure;

A direct white-light-emitting coordination polymers with tunable green–white photoluminescence by variation of counterion by Javier Vallejos; Iván Brito; Alejandro Cárdenas; Michael Bolte; Jaime Llanos; Matías López-Rodríguez; Víctor Lavín; Inocencio R. Martín (14-20).
Two Ag(I) coordination polymers, namely [Ag(L)(NO3)] (1), [Ag(L)(CF3SO3)] (2) and {L = butane-1,4-diyl-bis(pyridine-3-carboxylate)}, have been synthesized and characterized by X-ray diffraction and FTIR spectra. The counter-ion in the Ag(I) salts plays fundamental roles in the formation of Ag(I) complexes having different crystal structures and thermal properties. The Ag(I) ions in (1) and (2) are both two-coordinate, but they are tetra-coordinate in (1). Complex (1) adopts the polymeric linear chain-like structure bridged by L, while (2) proved to be one-dimensional zigzag polymeric chain. For all compounds the chains are assembled into 2D sheets by hydrogen bonds interactions and for (2) are further packed into 3D network by π-π interactions. Complexes (1)–(2) in solid state display at room temperature photoluminescence in the visible region. Although these complexes have emission bands centred in similar wavelengths when are excited at 320 nm at 275 K, (1) emits white light (CIE coordinates 0.33, 0.38) with a maximum emission at 514 nm, meanwhile (2) emits greenish light (CIE coordinates 0.20, 0.51) with a maximum emission at 513 nm. Hence, the complexes [Ag(L)X] (X = NO3 , CF3SO3 ) are tunable from green to white based on the structural variation through the counterion change.A direct white-light-emitting coordination polymers.Display Omitted
Keywords: Silver; White-light-emitting; Coordination polymers; X-ray; Flexible ligand;

Mixed CoN4Cl2 and CoCl4 units versus two CoN2Cl3 units in [Co2(Htbi)2Cl4] isomers by Zhi-Kai Qi; Fu-Qiang Zhang; Ru-Xin Yao; Jun-Liang Liu; Xian-Ming Zhang (21-25).
The solvothermal reaction of CoCl2 and 2-(4-thiazolyl)-benzimidazole (Htbi) in ethanol solution at 160 °C and 72 h gave rise to a majority of green crystals of [Co2(Htbi)2Cl4] 1 and minor isomeric blue crystals of 2. Two isomers show quite different isolated dinuclear structures bridged by two chlorides. Complex 1 consists of edge-sharing CoN4Cl2 octahedron and CoCl4 tetrahedron, while 2 is composed of two edge-sharing CoN2Cl3 square pyramids. The intra- and inter-molecular halogen hydrogen bonds play an important role at the stabilization in the solid state. Density functional theory calculations manifest that the optimized geometric parameters match very well with the experimental ones for both isomers. The difference of calculated Gibbs free energies demonstrates that intrinsic stability of 1 is superior to 2, in agreement with their relative yields under experimental conditions. The experimental UV–vis absorption spectra in N, N-dimethyl acetamide for 1 and 2 show the same absorption bands and match the computed results. Magnetic studies of 1 reveal that strong antiferromagnetic interactions were detected between octahedral and tetrahedral Co(II) atoms.The rare geometric isomerism in a pair of dinuclear complexes is reported. The computed Gibbs free energy difference is 4.52 kcal/mol. The high energy isomer 2 can transform into more stable 1 in DMA solution.Display Omitted
Keywords: Isomerism; Dinuclear; UV–vis; DFT;

Two thorium benzoate polytypes (I- and II-Th[O2C-C6H5]4) have been identified. The I-type has been hydrothermally (H2O; 210 °C for 20 h) or solvothermally (THF; 130 °C for 36 h) synthesized as a pure phase, from the association of thorium salt (chloride or nitrate) with the monotopic ligand, benzoic acid. The second is obtained from a mixture of thorium chloride and THF in the presence of small amount of water (H2O/Th = 15) after heating at 130 °C for 36 h. For the latter batch, the resulting white powder is composed of a mixture of I and II polytypes. Single-crystal X-ray diffraction analyses revealed that the thorium benzoates consist of the similar assembly of infinite chains of square antiprismatic units (ThO8) linked to each other through four bidentate carboxylates on each square face of the ThO8 moieties. They only differ by the β angle of the monoclinic crystallographic cell, which induces shift of the chain to each other in the I and II forms. Thermogravimetric analysis of I-Th[O2C-C6H5]4 indicated a two step weight loss from 280 up to 465 °C. It is assigned to the decomposition of the organic part together with the possible formation of thorium carbonate. The final residue after 465 °C is thorianite, ThO2.Two polytypes of thorium benzoates (I- and II-Th[O2CC6H5]4) have been isolated from hydrothermal of solvothermal routes (THF or THF/water mixture). Their structures are based on the assembly of infinite ribbons of thorium-centered square antiprismatic unit linked to each other through bridging carboxylate arms of the benzoate ligands.Display Omitted
Keywords: Coordination polymer; Thorium; Benzoic acid; Hydro/solvo-thermal synthesis; Single-crystal; X-ray diffraction analysis;

Studies on the photoredox behavior of copper(II) acetato complexes with tripodal 4N ligands in methanol solution by Christa Hirtenlehner; Elisa Tordin; Uwe Monkowius; Manuela List; Günther Knör (31-33).
The reactivity of copper(II) acetate complexes carrying the fully methylated tris(2-aminoethyl)amine ligand Me6tren under UV- and visible-light irradiation was studied in methanol solution. In the presence of water, the formation of colloidal copper nanoparticles occurred, indicating an irreversible decomposition of the copper(II) precursor under UV-light exposure. In dry methanol, a photoredox reaction involving the acetate ligand was observed, which leads to intermediate copper(I) complex formation. The potential of these processes for photocatalytic applications is briefly discussed and evaluated.The photoreactivity of copper(II) acetato complexes carrying the methylated tris(2-aminoethyl)amine ligand Me6tren was studied in methanol solution. In the presence of water, copper nanoparticles were formed. In dry methanol, charge transfer (LMCT) excitation leads to an intermediate copper(I) complex formation. Display Omitted
Keywords: Copper; Tripodal ligands; Carboxylates; Photolysis; Nanoparticles;

Two sandwich-like frameworks with Ag(I) and mixed ligands, [Ag3(bpp)3(ctc)·16H2O]n (1) and [Ag3(bpe)3(btc)·12H2O]n (2) (where bpp = 1,3-bis(4-pyridyl)propane, H3ctc = 1,3,5-cyclohexanetricarboxylic acid, bpe = 1,2-bis(4-pyridyl)ethane, and H3btc = 1,2,4-benzenetricarboxylic acid), have been synthesized and structurally characterized. Fully deprotonated tricarboxylate ctc3 − in 1 or btc3 − in 2, serves as anionic template driving more water molecules to aggregate into different morphologies of polymeric clusters. In 1, the hydrogen-bonding association of sixteen lattice water molecules leads to the formation of 2D layered water, which is composed of three kinds of units including planar (H2O)4, ladder-like (H2O)8 and windmill-shaped (H2O)20 cluster. One novel 1D double-comb-like water aggregate constructed from alternating (H2O)22 cluster and water dimmer exists in 2. The present observations suggest that anionic templates with more carboxylate groups have high tendency of being hydrated and make polymeric clusters possible.By employing tricarboxylate as anionic templates, we trap and characterize two different polymorphic water clusters including an infinite 2D-layered water and 1D double-comb-like water aggregate in two silver-based coordination polymers.Display Omitted
Keywords: Sandwich-like frameworks; Polymeric water clusters; 2D water layer; 1D water aggregate;

First 3D coordination polymer built from Ho(III) and 2-aminoterephthalate ligand by Miroslav Almáši; Vladimír Zeleňák; Ladislav Galdun; Juraj Kuchár (39-42).
Novel three-dimensional (3D) coordination polymer {[Ho23-ATA)24-ATA)(H2O)4]·2DMF·1/2H2O}n (1), built from Ho(III) cations and 2-aminoterephthalate anionic ligands (ATA2 −) was prepared and studied. The compound 1 contains 1D structural channels with the size 4.1 × 6.8 Å2, which propagate along b crystallographic axis. The channels are filled with the solvent molecules. The Ho(III) atom is eight-coordinated with distorted square anti-prismatic geometry. Complex was characterized by single crystal X-ray diffraction, thermogravimetry coupled with simultaneous evolved gas analysis using mass spectrometry (TG/DTG–DTA–EGA), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), solid-state UV–VIS spectroscopy and nitrogen adsorption at 77 K. After the desolvation the 1D structural channels collapse. The process is accompanied by structure transformation, however, according to the TG–DTA–EGA results, the Ho–ATA polymeric framework is stable up to 450 °C.The graphical abstract shows the view on the structure of novel three dimensional coordination polymer {[Ho23-ATA)24-ATA)(H2O)4]·2DMF·1/2H2O}n. In addition, the UV–VIS spectra of this compound and 2-aminoterephthalic acid are shown.Display Omitted
Keywords: Holmium(III); 2-Aminoterephthalate; Crystal structure; Thermal analysis; Spectral properties;

A new Keggin polyoxotungstate-based complex, [Cu(pz)]3[PW12O40] (pz = pyrazine, 1), has been synthesized and characterized by elemental analyses, IR, TG, and X-ray single crystal diffraction. In complex 1, one Keggin polyoxoanion coordinated with six copper cations to form an interesting one-dimensional chain, which was further linked by arrays of Cu(pz)n n + polymeric chains to construct high dimensional network. Topological analysis reveals that complex 1 exhibits a (4, 6)-connected three-dimensional framework with new topology (46  · 47)3 (46  · 66  · 83). Complex 1 shows good photocatalytic activity for the photodegradation of methyl orange in the presence of H2O2 under UV light irradiation.A new complex constructed from Keggin polyoxoanions and CuI–pyrazine coordination polymers to form high dimensional network with new topology (46  · 47)3 (46  · 66  · 83).Display Omitted
Keywords: Cu–pyrazine chains; Keggin; Polyoxometalates; Photocatalytic;

Effective one-step removal-inertization of hazardous metals (Cd and Hg) by environmental friendly reagents by Maria Laura Mercuri; Angela Serpe; Luciano Marchiò; Flavia Artizzu; Davide Espa; Paola Deplano (47-50).
[HMe2pipdt]I3 (Me2pipdt = N,N′-dimethyl-piperazine-2,3-dithione, 1) is capable to quantitatively dissolve elemental Cd and Hg to produce in a one-step reaction the [CdI(Me2pipdt)2]I3 (2) and [HgI2(Me2pipdt)] (3) complexes. Crystals of 2 and 3 have been structurally characterized and crystallize in the P-1 and C2/c space group respectively. In 2 Cd(II) shows a coordination geometry intermediate between the square pyramidal and the trigonal bipyramidal. In 3 Hg(II) adopts a distorted tetrahedral geometry which involves a S,S chelating ligand and two iodine atoms in the coordination sphere. Vibrational spectroscopy findings are in agreement with structural results showing in the far-infrared region to be a diagnostic probe in recognizing triiodides.The non-cytotoxic reagent [HMe2pipdt]I3 (Me2pipdt = N,N′-dimethyl-piperazine-2,3-dithione) has shown to be effective in removing and inerting quantitatively elemental cadmium and mercury, very toxic metals, under mild conditions, giving in a one-step reaction the [Cd(Me2pipdt)2I]I3 and [Hg(Me2pipdt)I2] complexes, respectively.Display Omitted
Keywords: Mercury; Cadmium; S ligand; Complex; X-ray;

Two lead (II) trisphosphonates, [Pb3(H3L1)2(H2O)] (1) and [Pb5(HL2)(H3L2)(H4L2)(H2O)2][(H2O)2] (2), have been synthesized from two trisphosphonate ligands and characterized by EA, IR, UV–vis, TGA, powder and single-crystal X-ray diffraction methods. The single-crystal X-ray diffraction analyses reveal that they both feature three-dimensional framework structures. The lead (II) ions are mainly five-coordinated, forming square pyramid coordination geometry. Although the two trisphosphonate ligands are very similar, different coordination modes and conformations are observed for them, suggesting that attachment of methyl groups to the central benzene ring has a major effect on the structure formation. They both absorb below 325 nm and are thermally robust.Two new lead (II) trisphosphonates, [Pb3(H3L1)2(H2O)] (1) and [Pb5(HL2)(H3L2)(H4L2)(H2O)2][(H2O)2] (2), have been synthesized and thoroughly characterized. They have different three-dimensional framework structures, suggesting that the attachment of methyl groups has a major effect on the structure formation. The TGA measurements reveal that they have similar thermal behaviors.Display Omitted
Keywords: Phosphonates; Lead; Crystal structure; Characterization;

A series of one-dimensional coordination polymers assembled from LnNO3  · 6H2O (Ln = Sm(1), Eu(2), Tb(3), La(4), Ce(5), Pr(6), Nd(7), Dy(8)), quinoline-2,3-dicarboxylic acid (2,3-H2qldc) and 1,10-phenanthroline (phen) formulated as [Ln(2,3-qldc)(3-qlc)(phen)]n (3-Hqlc = quinoline-3-carboxylic acid) were obtained under hydrothermal conditions. It is remarkable that in situ hydrothermal decarboxylation was observed during preparing these polymers. Complexes 18 were characterized by elemental analyses, IR spectroscopy and single crystal X-ray diffraction analyses. The thermal stabilities and photoluminescence properties of these complexes have been investigated.A series of lanthanide (III) coordination polymers with intriguing structures based on quinoline-2,3-dicarboxylic acid, quinoline-3-carboxylic acid and 1,10-phenanthroline ligands have been hydrothermally synthesized. The thermal stabilities and photoluminescence properties of these complexes have been investigated.Display Omitted
Keywords: Quinoline-2,3-dicarboxylic acid; 1,10-Phenanthroline; Lanthanide (III); Crystal structure; Photoluminescence;

An anthracene-based fluorescent sensor for sequential detection of zinc and copper ions by Hong Gyu Lee; Kyung Beom Kim; Gyeong Jin Park; Yu Jeong Na; Hyun Yong Jo; Seul Ah Lee; Cheal Kim (61-65).
Sequential recognition of Zn2 + and Cu2 + by a new anthracene-containing dipyridylamine-based receptor 1 (N-((anthracen-9-yl)methyl)-N-(pyridin-2-yl)pyridin-2-amine) has been achieved. Receptor 1 exhibited highly selective and sensitive fluorescence “off–on” recognition property to Zn2 + with a 1:1 binding stoichiometry. The resulting 1-Zn2 + complex displayed high selectivity to Cu2 + through the decrease in fluorescence intensity, demonstrating that 1-Zn2 + could detect Cu2 + via metal displacement. The sequential recognition of Zn2 + and Cu2 + via metal exchange suggests that receptor 1 has a potential utility for Zn2 + and Cu2 + detection.The sequential recognition of Zn2 + and Cu2 + by a new antracene-containing dipyridylamine-based receptor 1 (N-((anthracen-9-yl)methyl)-N-(pyridin-2-yl)pyridin-2-amine) has been achieved. Receptor 1 exhibited highly selective and sensitive fluorescence “off–on” recognition property to Zn2 + with a 1:1 binding stoichiometry. The resulting 1-Zn2 + complex displayed high selectivity to Cu2 + through the decrease in fluorescence intensity, demonstrating that 1-Zn2 + could detect Cu2 + via metal displacement.Display Omitted
Keywords: Anthracene; Fluorescence; Zinc ion; Copper ion; Metal displacement;

Tetranuclear complexes, [Fe4(HL)4](ClO4)4·5H2O (1) and [Mn4(HL)4](ClO4)4·2MeCN·2H2O (2) with [2 × 2] rectangle and square grid structure were self-assembled using the flexible ligand, 1,5-bis(1-(pyridine-2-yl)ethylidene)carbonohydrazide. The structures and magnetic properties were characterized by single crystal X-ray diffraction and variable temperature magnetic susceptibility measurements, respectively. For 1, the iron(II) centers are in distorted octahedral environment with N4O2 or N5O coordination spheres through two bridging enolyl oxygen atoms and two bridging N-N single bonds. Whereas, for 2, all four manganese(II) centers are in a distorted octahedral geometry with N4O2 coordination spheres through enolyl oxygen atoms connecting two adjacent metal ions. The magnetic properties of 1 and 2 show intramolecular antiferromagnetic exchanges.Tetranuclear complexes, [Fe4(HL)4](ClO4)4·5H2O (1) and [Mn4(HL)4](ClO4)4·2MeCN·2H2O (2) with [2 × 2] rectangle and square grid structure were self-assembled using the flexible ligand 1,5-bis(1-(pyridine-2-yl)ethylidene)carbonohydrazide. Complex 1 and 2 exhibit intramolecular antiferromagnetic exchanges.Display Omitted
Keywords: Iron(II); Manganese(II); Tetranuclear complexes; Crystal structures; Magnetic properties;

Metal cation-dependent construction of two 3-D interpenetrating networks based on the ligand 1-(4-carboxyphenyl)-1,2,4-triazole by Teng Li; Xiang Liu; Zhuang-Peng Huang; Qiang Lin; Chu-Ling Lin; Qing-Guang Zhan; Xiang-Dong Xu; Yue-Peng Cai (70-74).
Two d10 metal–organic frameworks (MOFs) with 1-(4-carboxyphenyl)-1,2,4-triazole (Hcpt), namely [Zn(cpt)2]n(1) and {[Cd(cpt)2] · 2DMF}n (2), have been solvothermally synthesized by fine control over synthetic conditions, and structurally characterized. The results reveal that compound 1, once reported in literature, crystallizes in the acentric Cc space groups, in which the tetrahedral Zn2 + center in 1 coordinates to two triazole nitrogen atoms and two carboxylate oxygen atoms from four μ 2  −  η 1:η 1 bridging cpt ligands, leading to a noncentrosymmetric 5-fold interpenetrating diamondoid 3-D network. On the other hand, new compound 2 has orthorhombic and space group Pbc21, in which distorted octahedral Cd2 + center in 2 coordinates to two triazole nitrogen atoms and two carboxylate oxygen atoms from four μ 2  −  η 1:η 1:η 1 bridging cpt ligands, resulting in an interesting 4-fold interpenetrating diamondoid 3-D network structures containing 1-D channels with a cross section of 9.5 × 9.3 Å. Considering their different topological structures, the gas adsorption experiments of 2 were carried out, and the results show that 2 presents a selective adsorption of CO2 over N2/H2. Moreover, the fluorescent properties of compounds 1 and 2 were also studied.Two 3-D d10 MOFs 1-2 were metal cation-dependent, in which 1 is a 5-fold interpenetrating diamondoid network, while 2 is an interesting 4-fold interpenetrating diamondoid 3-D network structures containing 1-D channels presenting a selective adsorption of CO2 over N2/H2.Display Omitted
Keywords: Metal cation-dependent assemblies; Interpenetrating networks; 1-(4-carboxyphenyl)-1,2,4-triazole; Selective adsorption; Fluorescence;

One-pot synthesis of self-assembled heteroleptic palladium(II) complexes with tmeda: An application of ligand exchange reactions by Sreenivasulu Bandi; Niladri Bihari Debata; Venkatachalam Ramkumar; Dillip Kumar Chand (75-78).
One-pot synthesis of self-assembled heteroleptic complexes of general formula [Pdx(tmeda)x(L)y](NO3)2x is achieved by combining required amount of tmeda, a chosen ligand L and Pd(NO3)2 under suitable reaction conditions. The strategy is devised using our understanding of a special variety of ligand exchange reactions (LER) around palladium(II) centers as modeled in this work. The one-pot synthesis technique is thus considered as an application of the unique LER.One-pot synthesis of self-assembled heteroleptic complexes of general formula [Pdx(tmeda)x(L)y](NO3)2x is achieved by combining required amount of tmeda, a chosen ligand L and Pd(NO3)2 under suitable reaction conditions.Display Omitted
Keywords: Palladium(II); Self-assembly; Ligand exchange reaction; One-pot synthesis;

A new sandwich mixed (phthalocyaninato) (porphyrinato) europium triple-decker (TPP)Eu2[Pc(OPh)8]2 (1), [TPP = dianion of 5,10,15,20-tetrakisporphyrin; Pc(OPh)8  = dianion of 2,3,9,10,16,17,23,24-octa(phenoxy)phthalocyanine], has been synthesized and characterized by a series of spectroscopic methods including MALDI-TOF mass spectrometry, 1H NMR spectroscopy, electronic absorption and infrared spectroscopy. The electrochemical property of 1 has been studied by cyclic voltammetry. Constructing the target triple-decker by coordination bonding between an europium ion and isoindole/tetrapyrrole nitrogen atoms from n-type double-decker (Eu[Pc(OPh)8]2) and p-type porphyrin (H2TPP) units, not only ensures the good solubility in conventional organic solvents, but more importantly successfully tunes the HOMO and LUMO levels into the range of ambipolar organic semiconductors required on the basis of electrochemical studies over 1. Using a solution-based quasi-Langmuir–Shäfer (QLS) method, the thin solid films of 1 were fabricated. The structure and properties of the thin films were investigated by UV–vis absorption spectra, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Experimental results indicated the film crystallinity and general molecular order for (TPP)Eu2[Pc(OPh)8]2 molecules in the QLS films. Organic thin-film transistor (OTFT) fabricated from the QLS films of 1 was revealed to show ambipolar properties that have never been revealed for devices fabricated from a single-phthalocyanine/porphyrin mixed component using solution processable technique, with the highly balanced mobilities for holes and electrons of 0.04 cm2  V− 1  s− 1 and 0.08 cm2  V− 1  s− 1, respectively.Display Omitted
Keywords: Phthalocyanine; Porphyrin; Triple-decker; Ambipolar; OTFT;

The reaction of dimethyl 5-(prop-2-ynyloxy)isophthalic acid, meso-alpha, and beta-di (4-pyridyl) glycol with ZnCl2 in a methanol aqueous solution affords MOF Zn−DPPG. The enantiomeric Zn−Fun1 and Zn−Fun2 were obtained through a strategy of in situ click reactions of Zn–DPPG with two opposite chiral adducts. With the l- or d-proline chiral functionality, the two Zn−Funs exhibited remarkable catalytic activities in the relative asymmetric aldol reactions, leading to the formation of opposite enantiomorphs, respectively.Two enantiomeric metal–organic frameworks, having opposite chiral functionality, were achieved through in situ click reactions within the same preassembled achiral Zn–MOFs. The enantiomeric MOFs exhibited remarkable catalytic activities in the relative asymmetric aldol reactions with the formation of opposite enantiomorphs.Display Omitted
Keywords: Click; Metal–organic framework; Postsynthesis; Aldol catalysis;

A facile fluorescent probe based on coumarin-derived Schiff base for Al3 + in aqueous media by Yan-Ge Zhang; Zhao-Hua Shi; Li-Zi Yang; Xiao-Liang Tang; Yan-Qing An; Zheng-Hua Ju; Wei-Sheng Liu (86-89).
A facile coumarin-based Schiff base sensor, 7-hydroxy-8-((2-hydroxy-phenylimino)methyl)-coumarin (H2L), has been designed and synthesized for selective detection of Al3 + in methanol–water (1:1, v/v). A fluorescence enhancement of 12-fold at 528 nm can be realized upon addition of 5.0 equiv. Al3 + with excitation at 421 nm. The mechanism of C=N isomerization, coupled with photoinduced energy transfer, is proposed to explain the observed spectral response. Most importantly, this Al3 + sensor has good water-solubility and can be excited with light in the visible range.A new coumarin-based Schiff base that shows high selectivity for Al3 + in methanol–water (1:1, v/v) has been achieved.Display Omitted
Keywords: Coumarin-derived; Schiff base; Fluorescent chemosensor; Water-solubility;

An unprecedented (3, 4)-connected self-penetrating metal–organic framework by Rong Hua; Xiao Liu Wu; Jin Ying Li; Lei Shi; Feng Luo (90-93).
In this work, we obtained a highly rare three-dimensional Zn(II) MOF, namely [Zn2(BTC)2(L)][(Me2NH2)2]·DMF (BTC3 −  = 1,3,5-benzenetricarboxylate, L = N1,N4-bis(pyridin-3-ylmethyl)cyclohexane-1,4-dicarboxamide), and Me2NH2  = dimethylamine cation) by solvo(hydro)thermal method. This polymer was characterized by single-crystal X-ray diffraction, thermogravimetry and solid-state luminescence analysis. The outstanding structural feature of it is (3, 4)-connected net with unprecedented (6 · 82)(6 · 85)(62  · 10)(62  · 83  · 10) topology and self-penetrating motif.We present here a new flexible, acylamide ligand to construct (3, 4)-connected net. The resultant presents a previously unobserved topology matrix featuring (6 · 82)(6 · 85)(62  · 10)(62  · 83  · 10) topology symbol. Moreover, the self-penetrating structure and the potential porosity in 1 is still notable.Display Omitted
Keywords: MOFs; Solvo(hydro)thermal method; (3, 4)-connected; Self-penetrating;

Syntheses and characterizations of zinc phosphites with new templates generated by N-alkylation transformations by Guo-Ming Wang; Ji-Qing Jiao; Xiao Zhang; Xiao-Meng Zhao; Xue Yin; Zong-Hua Wang; Ying-Xia Wang; Jian-Hua Lin (94-98).
Two new organically templated zinc phosphites, [tmpip]0.5[Zn2(HPO3)2(H2PO3)] (1) and [dmdabco][Zn3(HPO3)4]·(H2O) (2), have been synthesized under solvothermal conditions, where tmpip = N,N,N′,N′-tetramethyl-piperazinium and dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane. Note that the templating agents tmpip2 + and dmdabco2 + originated from in situ N-methylation transformations between CH3OH solvent and corresponding cyclic aliphatic amine precursors, i.e. piperazine, 1-methylpiperazine or 1,4-dimethylpiperazine in 1, and 1,4-diazabicyclo[2,2,2]octane in 2. Distinct from conventional Eschweiler–Clarke methylation with excess formic acid and formaldehyde, such direct methylation transformation from methanol molecules is unique. Compound 1 consists of ZnO4 tetrahedra, HPO3 and HPO2(OH) pseudopyramids, exhibiting a complex double layered structure with 12-ring windows. Compound 2 is constructed from strictly alternating ZnO4 tetrahedra and HPO3 pseudopyramids, and possesses a (3,4)-connected interrupted architecture with intersecting 8- and 12-ring channels.Two new templates were generated in situ by direct N-methylation transformations between CH3OH and organic amines. Two organically templated zinc phosphites were synthesized and structurally characterized. Compound 1 possesses a double layered structure, while 2 exhibits a (3, 4)-connected interrupted 3D architecture.Display Omitted
Keywords: Zinc phosphite; N-alkylation; In situ; Crystal structure; 12-Ring channel;

Screening of biological response to l-methionine based complexes as antitumor agents by Natarajan Raman; Muthusamy Selvaganapathy; Raju Senthilkumar (99-105).
This work reports an effort to understand the role of amino acid with DNA interactions in binding of biologically imperative metallointercalators [Cu(II), Ni(II) and Zn(II)], incorporated by benzylidine-4-aminoantipyrine (L) and l-methionine (Met) ligands. Herein, the pre-clinical evaluations of synthesized amino acid mixed-ligand complexes, inflammatory response and analgesic activity, have been done. In vivo and in vitro anti-tumor functions of the complexes against Ehrlich ascites carcinoma tumor model have been investigated. All these metal chelates are strong SOD mimetic compounds and also behave as peroxyl radical scavengers. Towards non-cancerous cell line, Cu(II) complex exhibits very low toxicity. On the other hand all the complexes have been found to exhibit cytotoxic effects against cancerous cell lines with potency more than that of the widely used drug cisplatin and hence they have the potential to act as promising anticancer agents. Captivatingly, they are non-toxic to normal cell lymphocytes, revealing that they are selective in killing only the cancer cells.Anti-inflammatory and analgesic activities of amino acid based mixed-ligand complexes are carrird out. They exhibit better cytotoxic effect against EAC and human cancerous cell lines than cisplatin. They are non-toxic to normal cell lymphocytes.Display Omitted
Keywords: Metallointercalators; Inflammatory response; Analgesic activity; Anti-tumor functions; Radical scavengers;

Three new coordination polymers, namely, [ML(H2O)] n (M = Co (1), Zn (2)) and [CuL(DMF)] n (3), have been hydrothermally synthesized through the reaction of bifunctional ligand 5-((2-methyl-1H-imidazol-1-yl)methyl)benzene-1,3-dioic acid (H2L) with divalent cobalt, zinc and copper salts, and structurally characterized by elemental analysis, IR and X-ray diffraction. Both complexes 1 and 2 are two-fold interpenetration 3D frameworks. Complex 3 exhibits (3,6)-connected framework with (4.62)2(42.610.83) topology. Furthermore, UV–vis absorption spectra and powder X-ray diffraction (PXRD) were investigated as well.Three new metal–organic frameworks, namely, [ML(H2O)] n (M = Co (1), Zn (2)) and [CuL(DMF)] n (3) (H2L = 5-((2-methyl-1H-imidazol-1-yl)methyl)benzene-1,3-dioic acid, DMF = N,N′-dimethylformamide), have been hydrothermally synthesized. Both complexes 1 and 2 are two-fold interpenetration 3D frameworks. Complex 3 exhibits (3,6)-connected framework with (4.62)2(42.610.83) topology. Furthermore, UV–vis absorption spectra and powder X-ray diffraction (PXRD) were investigated as well.Display Omitted
Keywords: Coordination polymers; Bifunctional ligand; Two-fold interpenetration;

Two novel lanthanide complexes, [Nd2(L)6(bipy)(H2O)]n (1) and [Sm2(L)6(bipy)(H2O)]n (2) (HL = 3,5-bis(trifluoromethyl)benzoic acid, bipy = 2,2′-bipyridine), have been solvothermal synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, element analyses and powder X-ray diffraction. Single-crystal X-ray diffraction measurements reveal that the crystal structures are isostructural, crystallizing in the orthorhombic space group P-1 and they consist of linear tetrameric Ln4 units which are connected through carboxylate of L ligands into a one-dimensional (1D) zigzag chain and spread into 2D supramolecular (4,4) sql net. Furthermore, magnetic studies reveal antiferromagnetic behavior for complex 1. The luminescent properties of 2 were also studied.Two novel lanthanide complexes have been synthesized and characterized. The crystal structures are isostructural and they consist of linear tetrameric Ln4 units which are connected into a 1D zigzag chain and spread into 2D supramolecular (4,4) sql net. Furthermore, magnetic and luminescent properties were also studied.Display Omitted
Keywords: Crystal structures; Lanthanide complexes; Magnetic properties; Luminescent properties;

A new chemosensor 3 having D–A–D type architecture of benzo[2,1,3]thiadiazole acceptor and thiophene donor with azomethine pendant arm was synthesized and its metal recognition capability was studied over the first row transition metal series. Compound 3 showed colorimetric sensitivity and selectivity towards for Fe(II) and Fe(III). Change in the strength of intramolecular charge transfer (ICT) due to metal to ligand charge transfer (MLCT) is responsible for color change. It has been established using CV and NMR titration. The sensitivity of 3 is in the range of μM concentration that leads to the visual detection by changing color from yellow to orange.Benzo[1–3]thiadiazole containing D–A–D type compound 3 was synthesized by simple and straightforward synthetic strategy. It acts as selective colorimetric probe for iron. Change in the strength of intramolecular charge transfer (ICT) due to metal to ligand charge transfer (MLCT) is responsible for color change.Display Omitted
Keywords: Donor–acceptor; Intramolecular charge transfer; MLCT; Iron sensor; Azomethine;

A new Mn(II) compound, namely [Mn3(OABDC)2(H2O)4]n (1 H3OABDC = 5-oxyacetateisophthalic acid), has been synthesized through combination of H3OABDC and MnCl2 under solvothermal conditions. A single crystal X-ray analysis reveals that 1 is a complicated three-dimensional (3D) framework based on trinuclear [Mn3(COO)4] subunits, which can be simplified into a (3, 6)-connected ant network. Variable temperature magnetic investigation reveals that this compound exhibits antiferromagnetic behavior.Presented here is a new Mn(II) coordination polymer, namely [Mn3(OABDC)2(H2O)4]n (1 H3OABDC = 5-oxyacetateisophthalic acid), which represents a complicated 3D architecture based on trinuclear [Mn3(COO)4] clusters, and can be simplified into a (3,6)-connected ant topological network.Display Omitted
Keywords: Mn(II) compound; 5-oxyacetateisophthalic acid; Trinuclear cluster; Magnetic property;

A highly selective fluorescence turn-on and reversible sensor for Al3 + ion by Ya-Ju Chang; Pei-Ju Hung; Chin-Feng Wan; An-Tai Wu (122-125).
A simple Schiff-base receptor 1 was prepared. It exhibits an “off–on-type” mode with high sensitivity in the presence of Al3 + and shows a high association constant (5.89 × 106  M− 2) toward Al3 + in DMSO–H2O (4:6 v/v) solution. The addition of EDTA to receptor 1·Al3 + complex quenches the fluorescent intensity, indicating that receptor 1 serves as a reversible chemosensor.Receptor 1 exhibits an “off–on-type” mode with high sensitivity in the presence of Al3 + and shows a high association constant (5.89 × 106  M− 2) toward Al3 + in DMSO–H2O (4:6 v/v) solution.Display Omitted
Keywords: Chemosensor; Fluorescence; Turn-on; Schiff-base;

Two new metal complexes with mixed nitrogen-donor heterocyclic monocarboxylate and dicarboxylate ligands {[Co2(L)2(BDC)(H2O)]·2H2O·6DMF}n (1) and [Mn(L)(OX)0.5]n (2) (HL = 3,5-di(pyridine-4-yl)benzoic acid, H2BDC = 1,4-benzenedicarboxylic acid, H2OX = oxalic acid) have been prepared and characterized by single crystal and powder X-ray diffractions, IR, and thermogravimetric analyses. Crystallographic and topological analyses identify that both complexes have new framework topologies. Complex 1 is a (3,8)-connected 2-nodal 3D net with a point (Schläfli) symbol of (42.5)2(44.510.67.76.8), while 2 is a (4,5)-connected binodal net with a point (Schläfli) symbol of (42.63.8)(42.65.83). Furthermore, magnetic investigation shows that both complexes exhibit overall weak antiferromagnetic coupling between the adjacent metal centers.New Co(II) and Mn(II) coordination frameworks {[Co2(L)2(BDC)(H2O)]·2H2O·6DMF}n (1) and [Mn(L)(OX)0.5]n (2) have been prepared by reactions of ligands of 3,5-di(pyridine-4-yl)benzoic acid (HL), 1,4-benzenedicarboxylic acid (H2BDC) and oxalic acid (H2OX) with corresponding metal salt and characterized.Display Omitted
Keywords: Co(II) and Mn(II) complexes; Topologies; Crystal structure; Antiferromagnetic interactions;

Solvothermal synthesis, structures, and gas adsorption properties of two cadmium-organic frameworks by Kang Liu; Xu Han; Yongcun Zou; Yu Peng; Guanghua Li; Zhan Shi; Shouhua Feng (131-134).
Two cadmium-organic frameworks were synthesized, namely, [Cd(dptz)2]·{Cd[(NH2)2CS]4}·(NO3)4 (1, dptz = 3,6-di-(pyridin-4-yl)-1,2,4,5-tetrazine) and Cd(dpmtz)2 (2, dpmtz = 3,6-di-(pyridin-4-yl)-1,2-dihydro-1-mercapto-1,2,4,5-tetrazine). Compound 1 was obtained by the self-assembly of dptz, Cd(SPh)2 and thiourea under solvothermal conditions. Compound 2 was prepared through an in situ ligand reaction in which generated a new ligand dpmtz only by changing reaction temperature. Compound 1 and 2 were characterized by single-crystal X-ray structure determination, thermogravimetric analysis and powder X-ray diffraction studies. The adsorption behavior shows that compound 2 has selective adsorption capacities of CO2 over N2.By changing the reaction temperature, we synthesize and characterize compound Cd(dpmtz)2 which shows selective adsorption behavior of CO2 over N2.Display Omitted
Keywords: Metal–organic framework; Tetrazine; Solvothermal reaction; Gas adsorption;

A novel mono-functionalized arylimido derivative of hexamolybdate bearing the electron-donating ethyl group, [Bu4N]2[Mo6O18(NAr)], has been synthesized by an improved reaction of octamolybdate ion with 4-ethylaniline hydrochloride using DCC (N,N′-dicyclohexylcarbodi-imide) as the dehydrating agent. Detailed assignments were achieved for the title compound by elemental analysis, IR, 1H NMR, UV–visible and single-crystal X-ray diffraction analysis. Preliminary antitumor activity test showed that the title compound has some effects on the cellular growth inhibition to K562 cells.Display Omitted
Keywords: Polyoxometalate; Organoimido derivatives; Mono-functionalization; Antitumor activity;

Coordination versatility of 1,5-bis(salicylidene)carbohydrazide in Ni(II) complexes by Manas Sutradhar; Tannistha Roy Barman; Eva Rentschler (140-143).
Versatile coordination behavior of a polydentate Schiff base ligand 1,5-bis(salicylidene)carbohydrazide (H3bsc) has been explored in Ni(II) complexes. [Ni(H3bsc)2](ClO4)2 (1)·H2O·3CH3CN is a bis chelate mononuclear complex of H3bsc in keto form, and [Ni4(H0.5bsc)2(O2CCMe3)3(CH3OH)4](2)·2H2O·2CH3OH is a tetranuclear complex of H3bsc with an unusual coordination. In 2, one phenolate group of the ligand coordinates in a monodentate way and the other coordinates in a μ 2-bridging mode to the Ni(II) center. This unusual coordination mode of the ligand stabilizes the Ni(II) complex in a tetranuclear form where the carbonyl oxygen of the ligand exists in between keto and enol form of bond order 1.5. Thus, complex 2, represents an unprecedented coordination behavior of the Schiff base ligand derived from carbohydrazides. Studies of magnetic properties of 2 are reported which reveal antiferromagnetic interaction between four Ni(II) centers.Fascinating coordination behavior of a symmetrical polydentate Schiff base ligand 1,5-bis(salicylidene)-carbohydrazide (H3bsc) has been explored in Ni(II) complexes. 1 is a bis chelate mononuclear complex of H3bsc in keto form and 2 is a tetranuclear complex with a very unusual coordination mode which shows antiferromagnetic exchange interactions.Display Omitted
Keywords: Ni(II); 1,5-Bis(salicylidene)carbohydrazide; X-ray structure; Antiferromagnetic interaction;

Syntheses and pharmacokinetics properties of an iloperidone pharmaceutical cocrystal by Ting-Ting Zhang; Hai-Tao Wang; Jiang-Tao Jia; Xiao-Qiang Cui; Qin Li; Guang-Shan Zhu (144-146).
We report here a pharmaceutical cocrystal, which was composed of iloperidone with 3, 5-pyridinedicarboxlic acid by crystal engineering strategy. It was characterized by single crystal X-ray and powder X-ray diffraction, which demonstrated that the cocrystal with high purity was obtained. Pharmacokinetics (PK) study of Jilin University China-Cocrystal 10 (JUC-C10) was performed to evaluate the advantages of this strategy for enhancing the oral absorption of the original active pharmaceutical ingredient (API) of iloperidone. The in vivo study of Beagle dogs revealed that the plasma concentration of JUC-C10 reached the maximum concentration and effective blood level earlier than the original API after oral administration, which suggested that JUC-C10 exhibited a more rapid absorption profile and could thus achieve a rapid onset of action.We report here a pharmaceutical cocrystal, which was composed of iloperidone with 3, 5-pyridinedicarboxlic acid by crystal engineering strategy. The in vivo study of Beagle dogs revealed that the plasma concentration of JUC-C10 reached to the maximum concentration and effective blood level earlier than the original API after oral administration.Display Omitted
Keywords: Pharmaceutical cocrystal; Single crystal X-ray diffraction; Powder X-ray diffraction; Pharmacokinetics;

Cerium-based tetranuclear polyhedra Ce-YB1 and Ce-YB2 assembled from lower symmetrical ligands without three fold axle, can work as molecular flasks to catalyze cyanosilylation reactions of aldehyde molecules with suitable sizes. The size-selectively catalytic behavior of the cages was investigated by using large aldehydes as the substrate, based on which the corresponding cyanosilylation reactions could not be carried out on the same condition.Cerium-based tetranuclear polyhedra Ce-YB1 and Ce-YB2 assembled from lower symmetrical ligands without three fold axle, can work as molecular flasks to catalyze cyanosilylation reactions of aldehyde molecules with suitable sizes.Display Omitted
Keywords: Cages; Molecular flask; Cyanosilylation;