Inorganic Chemistry Communications (v.25, #C)

Contents List (iii-ix).

A novel metal–organic framework, namely, [Cu5(H2L)2(btb)2(OH)2]·3H2O (1), where H6L = 2,4,6-trimethylbenzene-1,3,5-tris(methylenephosphonic acid) and btb = 1,4-bis(1,2,4-triazol-1-yl)butane, has been prepared under hydrothermal condition. Compound 1 displays a 3D (3,8)-connected framework based on the pentanuclear Cu(II) units with (43)(46·618·84) topology. The thermogravimetric and photocatalytic properties of 1 have also been investigated.A novel three-dimensional (3,8)-connected metal–organic framework based on pentanuclear Cu(II) units and trisphosphonates, namely, [Cu5(H2L)2(btb)2(OH)2]·3H2O (1), has been hydrothermally synthesized, where the thermogravimetric and photocatalytic properties have also been discussed for the compound.Display Omitted► The reported compound is a 3D (3,8)-connected framework. ► The compound is based on pentanuclear Cu(II) unit and triphosphonic acid ligand. ► The thermogravimetric property of the compound has been investigated. ► The photocatalytic property of the compound has been studied in detail.
Keywords: Metal–organic framework; Triphosphonic acid; Pentanuclear; Photocatalysis; (3,8)-Connected;

A Wells–Dawson polyoxoanion-based hybrid compound containing a nonanuclear copper cluster by Xiang Wang; Jun Peng; Kundawlet Alimaje; Zhenyu Shi (5-9).
A Wells–Dawson type polyoxoanion-based hybrid compound, Cu9(μ 2-OH)4(μ 3-OH)2(H2O)8(Hptz)8(P2W18O62)2·30H2O (ptz = 5-(4-pyridyl)-tetrazolate) (1), has been hydrothermally synthesized and characterized by routine methods. In compound 1, a novel nonanuclear copper cluster is constructed from two tetranuclear [Cu4(μ 2-OH)(μ 3-OH)(Hptz)3]6 + moieties, linked to each other though one Cu4 ion with the aid of two μ 2-OH and two ptz ligands. Then the P2W18 polyoxoanions bridge the nonanuclear copper clusters into a 1D ladder-like chain, in which the polyoxoanions and nonanuclear clusters act as two sides and middle rail of the ladder, respectively. The 1D chain is extended to a 3D supramolecular structure via hydrogen bonding interactions. The electrochemical property and magnetic behavior of compound 1 have been studied.A Wells–Dawson polyoxoanion-based hybrid compound, containing a novel nonanuclear copper cluster, Cu9(μ 2-OH)4(μ 3-OH)2(H2O)8(Hptz)8(P2W18O62)2·30H2O was synthesized. The electrochemical property and magnetic behavior of compound 1 were investigated.Display Omitted► A new nonanuclear copper cluster was obtained. ► The Wells-Dawson polyoxoanions linked the copper clusters into a 1D chain. ► Electrochemical properties and magnetic behavior of the compound were investigated.
Keywords: Polyoxometalates; Nonanuclear copper cluster; Hydrothermal synthesis; Electrochemical property;

The synthesis, structure and magnetic property of a new coordination network {[Co2(bcp)2(bipy)]}n (1) (H2bcp = 1,3-bis(4-carboxy-phenoxy)propane and bipy = 4,4′-pyridine), are reported. Compound 1 shows two identical 2D layers with 22.48.65 topology which are interpenetrated in a parallel fashion, resulting in a twofold interpenetrating motif containing polyrotaxane and polycatenane characters. Magnetic susceptibility indicated the antiferromagnetic exchange interaction. The magnetic behavior of 1 can be explained by the tilts of local distortion axes.A new compound displays twofold interpenetrating 22.48.65 topology containing polyrotaxane and polycatenane characters. The magnetic behavior of binuclear Co(II) complex can be explained by the tilts of local distortion axes.Display Omitted► This topology of 1 represents a new type of 6-connection topology. ► The structure contains meanwhile polyrotaxane and polycatenane characters. ► The magnetic behavior of dinuclear Co(II) complex can be explained by the tilt of local distortion axes.
Keywords: Interpenetration; Carboxylate; Topology; Magnetism;

Two novel heterobimetallic coordination polymers, [Cd{Pt(nic)4}]n・5nH2O (Cd–Pt-1) and [Zn{Pt(nic)4}(H2O)4]n・nH2O (Zn–Pt-1) (nicH = nicotinic acid), were synthesized by a one-pot slow-evaporation reaction system in water. Single crystal X-ray analysis revealed that Cd–Pt-1 and Zn–Pt-1 are two-dimensional sheet frameworks with open pores and one-dimensional chain polymers, respectively. However, crystal structure of Cd–Pt-1 is not robust in air. Therefore, BET surface area (pore volume) of Cd–Pt-1 calculated by N2 gas adsorption measurement is very low and the value is 22.5 m2  g− 1 (0.00813 cm3  g− 1).Two novel heterobimetallic coordination polymers, [Cd{Pt(nic)4}]n・5nH2O (Cd–Pt-1) and [Zn{Pt(nic)4}(H2O)4]n・nH2O (Zn–Pt-1) (nicH = nicotinic acid), were synthesized by a one-pot slow-evaporation reaction system in water. Single crystal X-ray analysis revealed that Cd–Pt-1 and Zn–Pt-1 are two-dimensional sheet frameworks and one-dimensional chain polymers, respectively. Although crystal structure of Cd–Pt-1 has open pores for N2 or H2 gas adsorption, they are closed due to the loss of crystal structure by removal of guest molecules.Display Omitted► Two types of Cd–Pt and Zn–Pt coordination polymers with nicotinic acid ligand were synthesized and identified. ► Crystal structure of Cd–Pt coordination polymer is two dimensional sheet framework. ► Crystal structure of Zn–Pt coordination polymer is one-dimensional zig–zag chain structure. ► N2 and H2 gas adsorption properties of two Pt coordination polymers were investigated.
Keywords: Zn and Cd coordination polymers; Pt complex ligand; Crystal structure; Gas adsorption property;

The fluoride route to Lindqvist clusters: Synthesis and crystal structure of layered hexatantalate Na8Ta6O19·26H2O by Sergey N. Britvin; Oleg I. Siidra; Andriy Lotnyk; Lorenz Kienle; Sergey V. Krivovichev; Wulf Depmeier (18-20).
Alkali-induced hydrolysis of fluoro-complexes of Ta and Nb affords one-pot synthesis of well crystallized compounds containing Lindqvist hexatantalate [Ta6O19]8 − and hexaniobate [Nb6O19]8 − ions. As an example, Na8Ta6O19·26H2O, a polyoxometalate with a remarkably complex layered structure was synthesized using the new method. An advantage of the proposed synthetic approach is that it can be easily embedded into existing technological flowcharts for the processing of Nb and Ta allowing direct synthesis of polyoxometalates from inexpensive fluoride precursors.Alkaline hydrolysis of aqueous solutions of fluoro-complexes of Nb and Ta allows one-step preparation of Lindqvist hexatantalates and hexaniobates.Display Omitted► A new method for the synthesis of Ta and Nb Lindqvist polyoxometalates is reported. ► It is feasible for integration with existing Nb and Ta reprocessing technologies. ► The method is exemplified by the synthesis of layered hexatantalate Na8Ta6O19·26H2O.
Keywords: Polyoxometalate; Lindqvist ion; Hexatantalate; Hexaniobate; Fluoride;

By in-situ formation of the tetrazolate ligand, 5-(3-pyridyl)tetrazole (L′), two three-dimensional metalorganic frameworks [CuI(L′)Na]n (1) and [Cu3I2L′]n (2), have been one-pot synthesized and constructed by the heterometallic cation cluster (Cu2I2Na2)2 + and (Cu6I4)2 + cluster as ten connected nodes, respectively.Presented here are two high-connected metalorganic frameworks based on cationic Cu―I clusters.Display Omitted► The construction of two new MOFs with high-connected nodes. ► The observation of a (5,10)-connected fit topology network and new [Cu2I2Na2]2 + cation cluster. ► The observation of an unprecedented (3,10)-connected (43)2(418·624·83) net and [Cu6I4]2 + cation cluster.
Keywords: Metalorganic framework; Topology; Clusters; Tetrazole;

A phenanthrene based highly selective fluorogenic and visual sensor for Cu2 + ion with nanomolar detection limit and its application in live cell imaging by Sellamuthu Anbu; Sankarasekaran Shanmugaraju; Rajendran Ravishankaran; Anjali A. Karande; Partha Sarathi Mukherjee (26-29).
A new phenanthrene based chemosensor has been synthesized and investigated to act as highly selective fluorescence and visual sensor for Cu2 + ion with very low detection limit of 1.58 nM; this has also been used to image Cu2 + in human cervical HeLa cancer cells.A new phenanthrene based chemosensor has been synthesized and shown to act as highly selective fluorescence sensor for Cu2+ ion, and its application in live cell imaging has been explored.Display Omitted► Phenanthrene based fluorogenic chemosensor R has been synthesized. ► R displays selective sensitivity towards Cu2 + ions with low detection limit of 1.58 nM. ► R has also been used to image Cu2 + in human cervical HeLa cancer cells.
Keywords: Fluorogenic Cu2 + sensors; Visual sensors; Live cell imaging; Intracellular Cu2 + detection;

Air stable Ni(II) and Pd(II) complexes viz. [Ni(LS)(P(OEt)3)] (1), [Ni(LN)(P(OEt)3)] (2), [Pd(LS)(P(OEt)3)] (3) and [Pd(LN)(P(OEt)3)] (4) [where LS and LN are dianions of N–(2–mercaptophenyl)salicylideneimine and N–(2–mercaptophenyl)naphthylideneimine respectively] have been synthesized and characterized by analytical and spectral (electronic, FT–IR, 1H, 13C and 31P NMR) methods. The 1H–31P HMBC spectrum established the coupling of phosphorus with the azomethine proton of the Schiff base and the aliphatic protons of triethylphosphite. Novel Ni(II) and Pd(II) complexes exhibited good catalytic activity in Kumada–Tamao–Corriu and Suzuki–Miyaura coupling reactions respectively.Square planar Ni(II) and Pd(II) complexes containing tridentate salicylideneimine ONS donor ligand and triethylphosphite have been synthesized and characterized. Novel Ni(II) and Pd(II) complexes exhibited good catalytic activity in Kumada–Tamao–Corriu and Suzuki–Miyaura coupling reactions respectively.Display Omitted► Synthesis of Ni(II) and Pd(II) complexes with ONS donor ligand and P(OEt)31H–31P HMBC spectra was used to establish the connectivity of P with Ni/Pd center ► Ni(II) and Pd(II) complexes showed catalytic activity in C―C coupling reactions
Keywords: Nickel(II); Palladium(II); Triethylphosphite; Schiff base; Coupling reaction;

A six-connected 3-D framework [enH2]2[Cu(en)2]3[H2W12O42]·6H2O constructed from paratungstate-based polyoxometalate units by Yuye Li; Chunli Leng; Junwei Zhao; Sudi Chen; Pengtao Ma; Lijuan Chen (35-38).
An organic–inorganic hybrid paratungstate [enH2]2[Cu(en)2]3[H2W12O42]·6H2O (1) (en = ethylenediamine) has been hydrothermally synthesized by reaction of Na2WO4·2H2O with CuCl2·2H2O in the presence of en and structurally characterized by elemental analyses, IR spectroscopy, UV spectrum, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and X-ray single-crystal diffraction. It is worth pointing out that 1 exhibits the 6-connected 3-D framework with the long topological (O'Keeffe) vertex symbol 4·4·64·4·4·4·4·64·4·4·4·64·4·4·4 for the [Cu(en)2]3[H2W12O42]4 − node, which gives the short vertex (Schläfli) symbol of 41263. To the best of our knowledge, such 6-connected 3-D open-framework constructed from paratungstate clusters is for the first time observed in polyoxometalate chemistry.An organic–inorganic hybrid paratungstate [enH2]2[Cu(en)2]3[H2W12O42]·6H2O has been synthesized and displays the first six-connected 3-D architecture constructed from paratungstate-based polyoxometalate units and [Cu(en)2]2 + connectors.Display Omitted► The paratungstate-based polyoxometalate units ► The organic–inorganic hybrid paratungstate ► Six-connected 3-D framework constructed from paratungstate-based polyoxometalate units and [Cu(en)2]2 + connectors
Keywords: Polyoxotungstate; Paratungstate; Copper; Six-connected 3-D framework;

First donor stabilized-phosphenium copper(I) complexes by Eric Digard; Jacques Andrieu; Hélène Cattey (39-42).
The preliminary studies of coordination properties of one donor stabilized-phosphenium adduct have been explored in copper chemistry. The preparation as well as the characterization of first examples of donor stabilized-phosphenium copper(I) complexes is reported in the paper. Thus, the direct addition of CuBr.SMe2 to an equivalent amount of cationic P‐ligands (L 1 + or L 2 +)(PF6), with ▪ and ▪, following by a crystallization in acetonitrile/Et2O led to first copper complexes [(L 1,2 +)CuBr2 ] 1 and 3 and [(L 1,2 +)Cu+(NCMe)3 +](PF6 )2 2 and 4 in a 1:1 ratio. However, when DMF/Et2O mixture was used as crystallization solvent, a stable bromo-bridged copper(I) dimer 5 [(L 2 +)CuBr(DMF)]2 was obtained. Molecular structures of mono- and di-nuclear copper complexes 1 and 5 have been confirmed by X‐ray structure analysis.Synthesis and full characterization of the first donor stabilized-phosphenium copper complexes are described. Depending on the crystallization solvent, mono- and di-nuclear structures are selectively obtained.Display Omitted► Coordination properties of stable phospheniums ▪ are explored in copper chemistry. ► First carbene-phosphenium copper(I) complexes have been obtained from CuBr.SMe2. ► Mono- or di-nuclear structures are obtained according to the crystallization solvent.
Keywords: Phosphenium; Carbene; Donor–acceptor ligand; Copper(I) halide chemistry;

Co(II) and Zn(II) complexes based on 1-(5-tetrazolyl)-4-(1-imidazolyl)benzene (HL) and 1,4-benzenedicarboxylic acid (H2pbda): [Co2(L)2(pbda)(H2O)3] (1) and [Zn(L)(pbda)0.5] (2) have been prepared under hydrothermal conditions and characterized by single crystal and powder X-ray diffractions, IR, and thermogravimetric analysis. Complex 1 exhibits binodal (3,5)-connected 2D net structure with (3.52)(32.53.64.7) topology; while 2 is a binodal (3,4)-connected 2-fold interpenetrating 3D framework with dmc (4.82)(4.85) topology. The influence of coordination geometries of metal centers on the structures of resultant complexes is discussed. Moreover, magnetic property of 1 and luminescence of 2 were investigated.Two new complexes [Co2(L)2(pbda)(H2O)3] (1) and [Zn(L)(pbda)0.5] (2) with different structure were synthesized and characterized. The complexes exhibited metal-controlled structural diversity.Display Omitted► Cobalt(II) and Zinc(II) complexes were synthesized; ► The complexes exhibited metal-controlled structural diversity; ► Fluorescence and magnetic property.
Keywords: Co(II) and Zn(II) complexes; Structural characterization; Fluorescence property; Antiferromagnetic interaction;

Luminescent behavior and energy transfer in homometallic Eu and ion associating Eu–Zn complexes with a pentadentate ligand by Hai-Ping Wang; Shi-Chao Wei; Mei Pan; Kang Li; Zi Wang; Cheng Yan; Cheng-Yong Su (48-50).
A pentadentate ligand L (2-(2-((bis(pyridin-2-ylmethyl)amino)methyl)phenoxy) -N,N-diphenylacetamide) was self-assembled with Eu (NO3)3 or Zn (NO3)2/Eu (NO3)3 to give homometallic complex ([EuL(NO3)3], 1) or ion associating complex ([ZnL(NO3)]2·[Eu(NO3)5]·CH3CN, 2), respectively. The photoluminescent behavior and energy transfer process were studied in the two complexes by excitation in different ways, in which 2 shows Förster energy transfer mechanism.Förster energy transfer can happen in Eu–Zn ion associating complex.Display Omitted► Using the same pentadentate ligand, homometallic Eu and ion associating Eu–Zn complexes are obtained. ► Förster energy transfer can happen in Eu–Zn ion associating complex.
Keywords: Ion associating complex; Luminescence; Förster energy transfer;

A new 1-D extended vanadoborate containing triply bridged metal complex units by Jian Zhou; Xing Liu; Feilong Hu; Huahong Zou; Xiaojuan Li (51-54).
A new 1-D vanadoborate {[Na(H2O)4]3[V12B18O54(OH)6(H2O)]2}(H4tren)4·(H3O)·41H2O (1, tren = tris(2-aminoethyl)amine) has been hydrothermally synthesized and structurally characterized. 1 consists of 1-D polymeric anions {[Na(H2O)4]3[V12B18O54(OH)6(H2O)]2 17 −}n, protonated H4tren4 +, H3O+ ions and free H2O molecules. The [V12B18O54(OH)6(H2O)]10 − clusters (denoted on V12B18) are connected by three complex [Na(H2O)4]+ ions as bridges into 1-D chain. 1 is the only example of triply bridged vanadoborate units by three metal complex units. The magnetic susceptibility shows the antiferromagnetic interaction between VIV cations in 1.The [V12B18O54(OH)6(H2O)]10 − clusters are connected by three complex [Na(H2O)4]+ ions as bridges into 1-D chains. 1 is the only example of triply bridged vanadoborate units by three metal complex units.Display Omitted► The [V12B18O54(OH)6(H2O)]10 − clusters are connected by triply bridged [Na(H2O)4]+ ions into 1-D chain. ► 1 is the only example of the vanadoborates containing triply bridged metal complex units. ► The magnetic susceptibility shows the antiferromagnetic interaction between VIV cations in 1.
Keywords: Hydrothermal synthesis; Polyoxovanadium; Borate; Crystal structures;

Two novel copper (II) complexes 1 and 2 with Schiff base ligands derived from kaempferol and polyamines such as ethylenediamine and diethylenetriamine have been synthesized and characterized by elemental analysis, IR, UV–visible spectroscopy, 1H NMR, molar conductance measurements and molecular modeling studies. The interactions of complexes with DNA have been studied by absorption spectra, viscosity measurements and gel electrophoresis under physiological conditions. The experimental results indicated that two complexes could bind to CT-DNA via an intercalative mode. Noticeably, cleavage DNA (pUC 19) activity of the complex 2 is stronger than that of complex 1. The antimicrobial activities against Escherichia coli and Staphylococcus aureus of two complexes were evaluated by the minimum inhibition concentrations (MIC), which indicated that complex 2 possessed more active against E. coli.Two novel Copper (II) Complexes with schiff base ligands derived from kaempferol and polyamines were synthesized and characterized. The solution influence on complex formation was investigated by UV spectra. The interactions of complexes with DNA were studied. The antimicrobial activities of complexes were evaluated by the MIC.Display Omitted► Two Schiff base copper (II) complexes derived from kaempferol were synthesized. ► The solution influence on complex formation was investigated by absorption spectra. ► DNA binding and DNA cleavage activities of two complexes were studied. ► The antimicrobial activities of two complexes were also evaluated by the MIC.
Keywords: Kaempferol; Schiff base copper (II) complexes; DNA interaction; Antimicrobial activity;

Two new isostructural 2D compounds based on hexa-nuclear [Cu6 I(ptz)6] clusters and Keggin anions, [Cu6 I(ptz)6][H3XMo12O40]·2H2O (X = P for 1; As for 2) (ptz = 5-(4-pyridyl)-tetrazole), have been hydrothermally synthesized. The hexa-nuclear [Cu6 I(ptz)6] subunits are constructed from five [Cu2N4] units with a cycle connecting cycle mode and further connected by the ptz to form 1D chains. These adjacent 1D chains are further linked by the Keggin anions to construct the intriguing 2D networks.Two new isostructural 2D compounds based on hexa-nuclear [Cu6 I(ptz)6] cluster and Keggin anions have been hydrothermally synthesized. The [Cu6 I(ptz)6] subunits are connected by the ptz to form 1D chains, which are further linked by Keggin anions to construct the intriguing 2D networks.Display Omitted► Two new 2D POM-based compounds containing hexa-nuclear CuI clusters were obtained. ► The {Cu6(ptz)6} contains five [Cu2N4] cycles with a cycle connecting cycle mode. ► Compounds 1 and 2 are efficiency photocatalysts and potential electrocatalysts.
Keywords: Polyoxometalate; Hexa-nuclear CuI cluster; 5-(4-Pyridyl)-tetrazole ligand; Photochemical catalysis; Electrochemical properties;

Two kinds of chiral Mn(III) salen complexes were synthesized and directly immobilized on pyrolytic waste tire char (PWTC) without modification of any organosilicon, which was an economic support, having rich oxy functionalized groups inherently. The as-prepared heterogeneous catalysts were characterized by X-ray photoelectron spectra (XPS), N2 sorption, Fourier transform infrared spectra (FT-IR) and thermogravimetric analysis (TG), and possessed of good catalytic performance in asymmetric epoxidation of unfunctionalized olefins. They obtained higher enantiomeric excess (ee) values than that of homogeneous catalysts for asymmetric epoxidation of 1-phenylcyclehexene and could be recycled three times.Chiral Mn(III) salen complexes were synthesized and directly immobilized on pyrolytic waste tire char (PWTC) without modification of any organosilicon. The obtained heterogeneous catalysts showed high conversions and good enantioselectivities in asymmetric epoxidation of unfunctionalized olefins.Display Omitted► The pyrolytic waste tire char (PWTC) was firstly used as a support in asymmetric epoxidation. ► Chiral Mn(III) salen complexes directly immobilized on PWTC without any organosilicon were reported firstly. ► The heterogeneous catalysts showed great catalytic performance.
Keywords: Chiral Mn(III) salen complex; Pyrolytic waste tire char; Heterogeneous catalysts; Asymmetric epoxidation;

Synthesis, crystal structure and antitumor activities of the dimeric silicotungstate containing cobalt: Na5K7[{β-SiCo2W10O36(OH)2(H2O)}2] ·39.5H2O by Rongxin Tan; Xiaohong Pang; Hui Wang; Shuxin Cui; Yaping Jiang; Cheng Wang; Xiaohong Wang; Wenzhi Song (70-73).
The dimeric polyoxometalate Na5K7[{β-SiCo2W10O36(OH)2(H2O)}2] ·39.5H2O (1) was synthesized and characterized by elemental analysis, IR spectroscopy and thermal gravimetric analysis. A single-crystal X-ray analysis was carried out on the crystal (1) which crystallizes in the triclinic system, space group p ī, with a  = 13.231 Å, b  = 20.170 Å, c  = 21.513 Å, α  = 62.964°, β  = 89.866°, γ  = 78.325° and Z  = 1. The polyanion (1) consists of two {β-SiCo2W10O36(OH)2(H2O)}6− Keggin moieties linked via two OH bridging groups, leading to a dimeric silicotungstate containing four cobalt ions. The experiment of antitumor activities in vitro shows that the title compound (1) exhibits remarkable inhibitory actions on liver cancer cells (SMMC-7721) and ovarian cancer cells (SK-OV-3).The dimeric silicotungstate Na5K7[{β-SiCo2W10O36(OH)2(H2O)}2] ·39.5H2O consists of two {β-SiCo2W10O36(OH)2(H2O)}6− Keggin moieties linked by two μ3-OH, and exhibits remarkable inhibitory actions on liver cancer cells SMMC-7721 and ovary cancer cells SK-OV-3 in vitro.Display Omitted► A new dimeric silicotungstate Na5K7[{β-SiCo2W10O36(OH)2(H2O)}2]· 39.5H2O (1) has been synthesized. ► The crystal (1) consists of two {β-SiCo2W10O36(OH)2(H2O)}6− Keggin moieties linked by two μ3-OH. ► The result of antitumor activities shows that the compound of Co-containing (1) presents remarkable inhibitory actions on liver cancer cells SMMC-7721 and ovary cancer cells SK-OV-3 in vitro.
Keywords: Polyoxometalates (POMs); Cobalt; Crystal structure; Antitumor activity;

A novel 3D porous MOF [Cd3(ABTA)2(DMF) (H2O)2] (1) (ABTA = 3, 4′, 5-azobenzenetricarboxylate) has been successfully synthesized by solvothermal reaction of Cd(NO3)2 •4H2O with ABTA. Single-crystal X-ray diffraction result reveals that complex 1 possesses a complicated 3D open framework with two intercrossed 1D channels along [200] and [11–1]. The photoluminescence experimental results of the complex in different solvents indicate that complex 1 has potential application in recognizing small linear conjugated molecule.A novel 3D porous MOF [Cd3(ABTA)2(DMF) (H2O)2] (1) (ABTA = 3, 4′, 5-azobenzenetricarboxylate) has been successfully synthesized by solvothermal reaction of Cd(NO3)2•4H2O with ABTA. Single-crystal X-ray diffraction result reveals that complex 1 possesses a complicated 3D open framework with two intercrossed 1D channels along [200] and [11–1]. The photoluminescence experimental results of the complex in different solvents indicate that complex 1 has potential application in recognizing small linear conjugated molecule.Display Omitted► A novel MOF based on “Y-type” conjugated ligand has been synthesized. ► Complex 1 features a 3D open framework with an unusual (3,3,6)-connected topology. ► Complex 1 has potential application in recognizing small linear conjugated molecular.
Keywords: 3, 4′, 5-azobenzenetricarboxylate; 3D open framework; (3,3,6)-connected topology; Luminescent properties; Sensor;

In situ hydrothermal synthesis of 2D mercury(I)–organic framework from 3-aminopyrazine-2-carboxylic acid and mercury(II) acetate by Saeed Dehghanpour; Khadijeh Jahani; Ali Mahmoudi; Mojtaba Babakhodaverdi; Behrouz Notash (79-82).
A new mercury(I)–organic framework based on Hg2 2 + dumbbell, [Hg2(apca)2]n, 1, [apca = 3-aminopyrazine-2-carboxylate] has been synthesized from an in situ reduction reaction of mercury(II) acetate and 3-aminopyrazine-2-carboxylic acid under hydrothermal condition. 1 has been characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction and has shown a 2D-layer structure constructed from Hg2 2 + dumbbell and bridging 3-aminopyrazine-2-carboxylate, which features a (63) topological network. The 2D compound is further assembled by hydrogen bonds and C―H⋯N interactions into 3D supramolecular networks. Fluorescence property and thermogravimetric analysis of 1 were also investigated.A new mercury(I)–organic framework constructed from Hg2 2 + dumbbell and 3-aminopyrazine-2-carboxylate (apca) have been synthesized from an in situ reduction reaction of mercury(II) acetate and apca under hydrothermal condition. Single-crystal X-ray diffraction has shown a 2D-layer structure, which features a (63) topological network. The 2D compound is further assembled by hydrogen bonds and C―H⋯N interactions into 3D supramolecular networks. The strong pale blue fluorescence for compound 1 can be observed and thermogravimetry shows that the compound is stable up to 100 °C.Display Omitted► The in situ formation of Hg2 2 +‏ dumbbell from mercury(II) acetates ► 2D-layer structure constructed from Hg2 2 + and bridging 3-aminopyrazine-2-carboxylate ► Assembly of the 2D compound into 3D supramolecular networks ► Hydrogen bonds and C―H···N interactions
Keywords: Hg2 2 + dumbbell; 3-Aminopyrazine-2-carboxylic acid; Hydrothermal synthesis; Metal organic framework;

Lewis base-directed assembly of two cobalt-based metal-organic frameworks by Lei Su; Wen Zhao; Li-Juan Zhang; Xiao-Li Zhao (83-85).
The employment of different Lewis bases pyridine and 3,5-DMpy under solvothermal conditions gave rise to two isostructural three-dimensional metal-organic frameworks: Co2(py)2(L)(DMA)2 (1) and Co2(L)(DMA)4 (2) (H4L = 5-(3,5-dicarboxybenzoylamino)-isophthalic acid, py = pyridine, DMA = N,N-dimethylacetamide, 3,5-DMpy = 3,5-dimethylpyridine). Single-crystal X-ray analysis has shown that 1 furnishes two different types of one-dimensional channels occupied by bridging DMA and terminal pyridine molecules. Changing pyridine to 3,5-DMpy in the assembly procedure affords 2, in which the channels are filled with bridging and terminal DMA molecules exclusively.Lewis bases pyridine and 3,5-DMpy were employed to tune the pores of two isostructural MOFs: Co2(py)2(L)(DMA)2 (1) and Co2(L)(DMA)4 (2). The results suggest that the employment of noncoordinating base 3,5-DMpy instead of pyridine under similar reaction conditions will contribute to the enhancement of porosity.Display Omitted► New tetracarboxylate ligand H4was first developed. ► Catenation was circumvented via the use of H4. ► Controlover the porosity of the two MOFs was achievedvia use of Lewis bases. ► The results of this enrich the of synthesis of MOFs.
Keywords: MOFs; Lewis base; 5-(3,5-dicarboxybenzoylamino)-isophthalic acid;

The furan-2,5-dicarboxyl acid (FDA) is firstly utilized to the construction of MOFs, and the pillars are enlisted in the structural formation by the method of ligand-to-ligand. The pillar properties play an important role in final structure. The flexible bpp (1,3-bi(4-pyridyl)propane) results in the robust porous [Zn3·(FDA)3·bpp·H2O]·2H2O (1) with high thermal stability (~ 270 °C) and medium CO2 uptake (1.65 mmol/g, 273 K), and the rigid bipy (4,4′-bipyridine) in 3-/3-D interpenetrated [Zn·(FDA)·bipy]·2H2O (2).The metal ion, furan-2,5-dicarboxyl acid and ligand-to-ligand pillar are assembled into MOFs. The flexible bpp results in the robust porous 1 and the rigid bipy in 3-/3-D interpenetrated 2.Display Omitted► The furan-2,5-dicarboxyl acid is firstly utilized to the construction of MOFs. ► The pillars are enlisted in the structure by the method of ligand-to-ligand. ► The pillar properties play an important role in final structure. ► The bpp results in the robust porous 1 and the bipy in 3-/3-D interpenetrated 2.
Keywords: Metal–organic framework; Structural interpenetration; Pillar; Gas absorption;

Solvothermal synthesis of chromium(III) complexes with the ‘Bis–tris’ ligand by Kristoffer Graham; Laura E. Sharp; Lynne H. Thomas; Mark Murrie (89-91).
In methanol under solvothermal conditions, we show how the nuclearity of the complex can be tuned from a monomer [CrIII(H3L)Cl] (1) to a tetramer [CrIII 4(H2L)4] (2) with an unusual twisted {M4O4} core topology {Bis–tris, H5L = (HOCH2CH2)2NC(CH2OH)3}. The magnetic data for 2 can be fitted to a simple 1J model with J  = − 20.25(5) cm− 1.Tuning the solvothermal reaction conditions produces a new {Cr4} tetramer, possessing an unusual twisted {M4O4} core topology, with the tri-deprotonated Bis–tris ligand.Display Omitted► The nuclearity of the product can be tuned from monomer to {Cr4} tetramer. ► The tetramer has an unusual twisted {M4O4} core topology. ► Magnetic characterization of the tetramer reveals intramolecular antiferromagnetic exchange interactions.
Keywords: Chromium(III); Polydentate ligands; Solvothermal; Crystal structure; Magnetic properties;

A new three-dimensional (3D) metal–organic framework (MOF) {Zn53-OH)2(obb)4[(CH3)2NH]2}·2DMF (1; H2obb = 4,4′-oxybisbenzoic acid; DMF = N,N′-dimethyl formamide) with unusual Zn53-OH)2(COO)8 secondary building units (SBUs) has been solvothermally synthesized and structurally characterized by the aid of single crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Elemental analysis (EA) and Infrared Spectroscopy (IR). The unprecedented pentanuclear Zn53-OH)2(COO)8 SBU was formed by two trimeric Zn33-OH)(COO)6 SBUs, which can be simplified as 4-connected node. Correspondingly, compound 1 exhibits dia structural topology.Presented here is a new 4-connected dia zinc–organic framework with unusual Zn53-OH)2(COO)8 SBUs.Display Omitted► A new zinc–organic framework with unusual pentanuclear Zn53-OH)2(COO)8 SBUs ► Pentanuclear Zn53-OH)2(COO)8 SBU formed by two trimeric Zn33-OH)(COO)6 SBUs by sharing the Zn2 atom ► The observation of interesting double helix chain and 4-connected dia topology based on Zn53-OH)2(COO)8 SBUs.
Keywords: Metal–organic framework; Zinc; SBUs; Topology; Crystal structure;

Ligand-directed and solvent-controlled assembly of six novel functional supramolecular metal–organic frameworks by Xia Zhao; Xiao-Ping Ye; Li-Mei Chang; Chu-Jun Chen; Jin-Ying Gao; Shan-Tang Yue; Yue-Peng Cai (96-102).
Six novel functional metal–organic frameworks, namely, [CdCl(IP)(Hpydc)(H2O)]·2H2O (1), [Cd(IP)(H2imdc)]Cl (2), [Cd(IP)2(H2O)2](1,5-nds)·2H2O (3), [Co(IP)(H2O)4](1,5-nds)·H2O (4), [Zn(IP)(μ2-SO4)(H2O)]·H2O (5), [Zn(IP)(SO4)(H2O)3] (6) (IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline, H2pydc = pyridine-2,6-dicarboxylic acid, H3imdc = imidazole-4,5-dicarboxylic acid, 1,5-nds = 1,5-naphthanlenedisulfonate), were synthesized by controlling auxiliary ligands, metal centers and solvents. In compound 1, Cd(II) is chelated by IP and Hpydc ligands, forming 0D → 3D supramolecular structure. Compound 2 is a 1D chain with repeated [Cd(IP)]2+ units connected by H2imdc ligands. With different metal centers, compounds 3 and 4 possess different crystal structures. With solvents regulated, compounds 5 and 6 exhibit distinct structures. In compound 5, sulfate anions show μ2-bridging mode, which results in the formation of 1D chain. In compound 6, only one oxygen atom from sulfate anion coordinates to the metal center, resulting in discrete repeated units. The luminescent properties of 1, 2, 3, 5, 6 and thermal stabilities of all compounds were measured.Six compounds were synthesized by controlling extra ligands, metal centers and solvents.Display Omitted► Six novel supramolecular coordination polymers have been synthesized. ► Reaction conditions affect the structure of the six compounds. ► Five compounds exhibit luminescent properties.
Keywords: Supramolecule; Transition metals; Luminescence; Ligand-directed; Solvent-controlled;