Inorganic Chemistry Communications (v.41, #C)

Contents List (iii-ix).

A new 2D coordination polymer [MnII(pic)(4,4′ -azpy)(H2O)]ClO4·EtOH (pic = 2-picolinate) has been synthesized where each of the octahedral Mn(II) center is connected by trans coordinating 4,4′-azpy and syn-anti bridging picolinate, resulting in a sheet like structure. Density functional theory (DFT) calculations, at the BLYP-D3/def2-TZVPD level of theory, are performed to explore the interplay of various supramolecular interactions present within the coordination polymer.A new Mn(II) coordination polymer has been synthesized using a primary ligand 2-picolinic acid and a neutral secondary spacer 4,4′-azpy. The 3d framework of the complex is stabilized via several supramolecular interactions which have been studied by DFT calculations.Display Omitted
Keywords: Mn(II) picolinate complex; 4,4′-Azobis(pyridine); Crystal structure; Supramolecular interactions; Theoretical calculations;

Four new binuclear aluminum chloride complexes {(1)AlCl}2 (5), {(2)AlCl}2 (6), {(3)AlCl}2 (7) and {(4)AlCl}2 (8) have been prepared in good yields by alkane elimination from the reaction of AlEt2Cl and chiral biaryl-based N2O ligands, (S)-2-(pyridine-2-ylmethylamino)-2′-hydroxy-1,1′-binaphthyl (1H2), (S)-5,5′,6,6′,7,7′,8,8′-octahydro-2-(pyrrol-2-methyleneamino)-2′-hydroxy-1,1′-binaphthyl (2H2), (S)-5,5′,6,6′,7,7′,8,8′-octahydro-2-(pyridine-2-ylmethylamino)-2′-hydroxy-1,1′-binaphthyl (3H2) and (S)-2-(pyrrol-2-methyleneamino)-2′-hydroxy-6,6′-dimethyl-1,1′-biphenyl (4H2), which are derived from (S)-2-amino-2′-hydroxy-1,1′-binaphthyl or (S)-2-amino-2′-hydroxy-6,6′-dimethyl-1,1′-biphenyl, respectively. Complexes 58 have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. The complexes 58 have a similar C 2 quasi-symmetric ClN2AlO2AlN2Cl core structure, and they are active catalysts for the polymerization of rac-lactide in the presence of propylene oxide (PO), leading to the heterotactic-rich polylactides.A new series of binuclear aluminum complexes have been prepared from chiral biaryl-based N2O ligands. The aluminum complexes are active catalysts for the polymerization of rac-lactide, leading to the heterotactic-rich polylactides.Display Omitted
Keywords: 2-Amino-2′-hydroxy-1,1′-binaphthyl; N2O ligand; Chiral aluminum complex; Polymerization of lactide;

Nitric oxide species as oxidising agents and adducts for soft scorpionates by Rajeev Rajasekharan-Nair; Lisa Darby; John Reglinski; Mark D. Spicer; Alan R. Kennedy (11-13).
Bis-(κ3-H,S,S-dihydrobis-(methimazolyl)borato)ruthenium(II), [Ru(BmMe)2], has been prepared and tested as a nitric oxide scavenger using NO, NOBF4 and NOBr. The products isolated show that, NO and NO+ are good one electron oxidising agents towards the ruthenium complexes but NO is not coordinated to the metal. The oxidised species, [Ru(BmMe)2]BF4 has been isolated and characterised. Reaction of “Ru(NO)Cl3” with NaBmMe results in the removal of the borohydride from the ligand and formation of [Ru(mtH)3(mt)(NO)Cl]+.The reactions of bis-(κ3-H,S,S-dihydrobis(methimazolyl)borato)ruthenium(II), [Ru(BmMe)2], with nitric oxide species (NO, NOBF4 and NOBr) are investigated.Display Omitted
Keywords: Nitric oxide; Oxidising agent; Soft scorpionates; π-Acids;

[Zr(acac)4] underwent ligand exchanges with pentadentate Schiff base ligand of N,N′-bis(3-salicylidenaminopropyl)amine. Full characterization of this complex was accomplished with elemental analyses, spectroscopic studies (1H NMR, 13C NMR, FT-IR, UV–vis) and X-ray structure analysis. X-ray crystallography indicated that this complex had a dinuclear structure in which each seven coordinated zirconium atom adopted a distorted pentagonal bipyramid geometry that was joined to the second zirconium by a μ-oxo bridge. The catalytic activity of the prepared complex was investigated in the synthesis of indole derivatives under mild conditions. The results revealed that although in this complex Zr (IV) was surrounded by seven other atoms, it could still catalyze indole condensation reaction and lead to plausible yields of products.Molecular structure of a dinuclear Zirconium (IV) ComplexThe coordination sphere of the Zr1 can be described as distorted pentagonal-bipyramidal.A single-crystal X-ray structure of this compound proves that the complex is a centrosymmetric dinuclear unit in the solid state consisting of two mononuclear zirconium containing ligands that are joined by a μ-oxo bridge.Display Omitted
Keywords: Zirconium; Schiff base; Catalyst; Crystallography;

The slow diffusion reactions of a double-betaine-containing ligand with YbH[SiMo12O40]·nH2O and Ca2[SiMo12O40]·nH2O led to the isolation of two new organic–inorganic hybrid assemblies, [Yb(O)(HL)2(H2L)0.5(H2O)3][SiMo12O40]·2.5CH3CN·1.5H2O (1) and [Ca(HL)2(L)0.5(H2O)4] [SiMo12O40]·5CH3CN·H2O (2) (L = 1,4-bis(pyridinil-4-carboxylato)-l,4-dimethylbenzene). Compounds 12 were characterized by elemental analyses, TG, IR, XPS and single-crystal X-ray diffraction. Compound 1 contains the dinuclear [(YbO)(HL)2(H2O)3]2 coordination moieties and discrete protonated L ligands, which are connected together by H-bonds and π–π interactions to form a 3D supramolecular framework with the Keggin-type [SiMo12O40]4 − polyoxoanions and solvent molecules encapsulated. Compound 2 possesses discrete [Ca(HL)2(L)0.5(H2O)4]2 coordination units that are linked by the extensive intermolecular H-bonds and π–π interactions to form a 3D supramolecular framework with the [SiMo12O40]4 − polyoxoanions and solvent molecules are encapsulated in the interbedded cavities. The structural motifs of the metal–organic coordination units can be obviously modulated by the use of chemically different cationic nodes. The degradation of Rhodamine-B (RhB) under UV irradiation with compounds 1 and 2 as heterogeneous photocatalysts were investigated, both exhibiting good photocatalytic properties. Furthermore, these hybrid compounds display luminescent properties induced by organic ligands.New organic–inorganic hybrid supramolecular frameworks based on metal–bis(betaine) coordination moieties and Keggin-type polyoxometalates (POMs) were assembled by changing metal cations.Display Omitted
Keywords: Polyoxometalate; Lanthanide; Alkaline earth metal; Betaine; Photocatalysis; Luminescence;

Through controlling the in-situ methoxyl addition that consequently switches the metal-chelation effect, a one-dimensional helical coordination polymer (1) and a chiral congeners ( P -2 and M-2) were prepared, the 41 helice of opposite chirality in complex 1 are stacked alternately to form a racemate, while the 41 and 43 helices in the other are assembled homochirally by metal-chelation effect to generate a conglomerate, P -2 and M-2, respectively.Through controlling the in-situ methoxyl addition that consequently switches the metal-chelation effect, a racemic one-dimensional helical coordination polymer and a chirality-resolved congener were isolated.Display Omitted
Keywords: Solvolysis; Chirality; Helicate; Crystal structure;

Fabrication of ITO glass supported Tb-MOF film for sensing organic solvent by Hailing Guo; Shujie Zhu; Dani Cai; Chenguang Liu (29-32).
Homogeneous nanosized Tb(BTC)(H2O) MOF was fabricated using sodium acetate, which has basicity (to increase nucleation rate) and capping groups (CH3COO) (to prevent crystal growth), as modulator. Following the successful preparation of the nanocrystals, an ITO glass-supported Tb-MOF film was prepared by dip-coating. This film exhibited highly sensitive and selective sensing of organic solvents. The probable sensing mechanism is discussed.Homogeneous nanosized Tb(BTC)(H2O) MOF was fabricated using sodium acetate as modulator. An ITO glass-supported Tb-MOF film was prepared by dip-coating, which exhibited highly sensitive and selective sensing of organic solvents.Display Omitted
Keywords: MOFs nanoparticles; MOFs film; Chemical sensors; Modulator;

4-Methoxypyridine N-oxide reacts with various silver(I) salts to consistently generate 1-D coordination polymers within which the ligand bridges one, two or three silver atoms. In all three structures described the counteranions are non-coordinating and there are subtle differences in the ways in which the polymers propagate along the 1-D chain.4-Methoxypyridine N-oxide reacts with various silver(I) salts to consistently generate 1-D coordination polymers within which the ligand bridges one, two or three silver atoms.Display Omitted
Keywords: Silver; N-oxide ligand; Crystal structure; Bridging ligand; Coordination polymers;

Four novel amino acid (l-isoleucine (ILe) and l-cysteine (Cys)) polyoxometalate nanotubes ((ILe)3PMo12O40·3H2O, (ILe)3PW12O40·3H2O, (Cys)3PMo12O40·3H2O, and (Cys)3PW12O40·3H2O) are successfully synthesized by solid-state chemical reaction method at room temperature. Elemental analysis, infrared spectroscopy and XRD analysis results prove that the samples still possess Keggin type structure. Transmittance electron microscopy (TEM) and scanning electron microscopy (SEM) have shown that the samples have nanotube structures with diameter about 20–200 nm and length of up to several micrometers.As shown in the figure, some materials have the morphology of tube and that the average length of the tubes is up to several micrometers, and the width of the tubes is in the range of 20–200 nm.Display Omitted
Keywords: Nanotube; Solid-state; Polyoxometalate; Amino acid;

An unprecedented binodal (4,10)-connected metal–organic framework based on pentanuclear cobalt(II) clusters by Jin-ming Hao; Li-na Wang; Kristof Van Hecke; Guang-hua Cui (43-46).
A three-dimensional Co(II) metal–organic framework {[Co5(btec)2(btx)(μ 3-OH)2(H2O)2] · 2H2O} n (1) (H4btec = 1,2,4,5-benzenetetracarboxylic acid, btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) containing rare pentanuclear Co(II)-clusters has been hydrothermally synthesized and structurally characterized, and shows an unusual binodal (4,10)-connected topology. The fluorescence properties and catalytic activity of the complex for degradation of methyl orange in the Fenton-like process were investigated.A three-dimensional Co(II) metal–organic framework {[Co5(btec)2(btx)(μ 3-OH)2(H2O)2]·2H2O} n (1) (H4btec = 1,2,4,5-benzenetetracarboxylatic acid, btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) containing rare pentanuclear Co(II)-clusters has been hydrothermally synthesized and structurally characterized, which shows an unusual binodal (4,10)-connected topology. The fluorescence property and catalytic activity of the complex for degradation of methyl orange dye in Fenton process were investigated.Display Omitted
Keywords: 1,2,4,5-Benzenetetracarboxylate; Catalytic property; (4,10)-Connected network; Pentanuclear Cobalt(II) Cluster;

Assembly of a POM-based hybrid compound consisting of both helical and interdigitated motifs by Shuhong Wang; Zhiyao Sun; Chunjing Zhang; Liang Ni; Cheng Wang; Yang Gao; Lili Lv; Jinhui Chang; Wenhui Hao (47-50).
A new compound, {[Ag(DF)2]4SiW12O40} (1), (DF = 4,5-diazafluoren-9-one), has been hydrothermally synthesized, and characterized by elemental analyses, IR, TG and single crystal X-ray diffraction. A structural feature in 1 is that the adjacent [Ag(DF)2]2(SiW12) fragments are linked together by H-bonds to achieve left- and right- handed helical chains with the pitch ca. 26.3 Å. Furthermore, these helical chains are linked via H-bonds forming a poly-pendant layer, in which the [Ag(DF)2] moieties as pendants are appended to the two sides of the layer. Interestingly, adjacent layers mutually engage in an interdigitated pattern to result in a novel a 2D + 2D → 3D architecture. The electrochemical studies show that 1 has a good electrocatalytic activity toward reduction of hydrogen peroxide molecules.Display Omitted
Keywords: Polyoxometalates; Helix; Interdigitation; Electrochemical properties;

C―O bond activation and subsequent decarbonylation of ester promoted by Fe(PMe3)4 by Yunqiang Lu; Xiaoyan Li; Lin Wang; Hongjian Sun (51-53).
The reactions of 8-quinolinyl esters with iron(0) complex supported by trimethylphosphine ligands afforded four hexa-coordinate chelate-[C,N] iron(II) carbonyl complexes 58 via Cacyl ―O bond activation and subsequent decarbonylation. Complexes 58 were characterized through IR, 1H NMR, 31P NMR and elemental analysis. The crystal structures of complexes 58 were determined by X-ray diffraction.The reactions of 8-quinolinyl esters with iron(0) complex supported by trimethylphosphine ligands afforded four hexa-coordinate chelate-[C,N] iron(II) carbonyl complexes 58 via Cacyl ―O bond activation and subsequent decarbonylation. The crystal structures of complexes 58 were determined by X-ray diffraction.Display Omitted
Keywords: C―O activation; Decarbonylation; Iron(0) complex; Trimethylphosphine;

From 1D chain to 2D layer and 3D network: Solvent-free syntheses of new metal oxalates by Tong Wu; Daibing Luo; Chunmei Duan; Zhonghua Shi; Yaoqiang Chen; Zhien Lin (54-57).
Four metal oxalates, Hdpa⋅Cr(ox)2 (1), (Hdpa)2⋅ Zn2(ox)3  ⋅ 2H2O (2), Zn(H2O)(ox) (3), and (Hgua)(H3O) ⋅ Cd(C2O4)2 (4), have been synthesized under solvent-free conditions, where dpa = diisopropylamine, ox = oxalate, and gua = guanidine. These compounds have extended structures varying from 1D chain (for 1), to 2D layer (for 2 and 3), and 3D framework network (for 4). The temperature dependence of the magnetic susceptibility of compound 1 indicates the existence of antiferromagnetic interactions between the chromium ions. Upon excitation at 230 nm, compound 3 exhibits an extensive luminescence with a peak centered at 501 nm.Four new metal oxalates have been synthesized under solvent-free conditions. These compounds display different structures varying from 1D chain to 2D layer and 3D framework.Display Omitted
Keywords: Solvent-free synthesis; Crystal structure; Coordination polymer; Oxalate; Luminescence;

One pillared-layer α-Po framework with a rare tetracobalt-formate (4,4) sheet exhibiting a field-induced magnetic transition by Zuo-Xi Li; Xiao-Feng Gou; Wanqi Jie; Gangqiang Zha; Tao Wang; Yadong Xu (58-61).
A novel coordination polymer has been synthesized under solvethermal reaction, which represents a pillared-layer α-Po framework with a rare tetracobalt-formate (4,4) sheet. The magnetic properties have been well studied, and the results show an antiferromagnet and field-induced magnetic phase transition for the title complex.A new pillared-layer α-Po framework associated with a rare tetracobalt-formate (4,4) sheet has been isolated from the solvethermal reaction. The magnetic researches on the title complex show an antiferromagnet and field-induced magnetic phase transition.Display Omitted
Keywords: Molecule-based materials; Formate ligand; Tetracobalt cluster; Pillared-layer framework; Magnetic property;

Cu(II)/oxalato coordination polymer with 3-pyridinepropanol (3-Hhpp) has been prepared and structurally characterized as [Cu2(3-Hhpp)4Br2(ox)]n. Its structure consists of neutral centrosymmetric oxalato bridged dinuclear Cu(II) entities. One of the two crystallographically independent 3-Hhpp ligands acts as an additional bridge between the dinuclear units giving rise to the formation of two dimensional layers. The magnetic susceptibility measurements revealed a strong antiferromagnetic interaction between the copper metal ions with J/k B  = − 243(2) K (with H  = − 2  J S Cu1·S Cu2). The strength of the exchange interaction is correlated with published magneto-structural data on related oxalato-bridged Cu(II) compounds and discussed on the basis of the structural features.New Cu(II) oxalate coordination polymer incorporating 3-pyridinepropanol as a bridging ligand has been prepared and its magnetic properties studied.Display Omitted
Keywords: Coordination polymer; Copper(II) oxalate; Magnetic properties; X-ray structure; Pyridinealcohol ligand;

One-dimensional butterfly and cubane argento-selenotungstate clusters bridged by bis(diphenylphosphino)ethane ligands by Hua-Tian Shi; Lu-Jun Zhou; Ai-Quan Jia; Xiang-Hong Huang; Qian-Feng Zhang (65-67).
Interaction of [Et4N]2[WSe4], AgBr and bis(diphenylphosphino)ethane (dppe) in a 1:2:1 ratio afforded the polymeric trinuclear cluster {[Et4N][(μ-Br)(μ 3-WSe4)Ag2(μ-dppe)]}n (1), while the similar reaction of [Et4N]2[WSe4], AgCl and dppe in a 1:3:1 ratio in the presence of [Et4N]Br gave the polymeric tetranuclear cluster {[Et4N][(μ 3-Br)(μ 3-WSe4)Ag3Cl(μ-dppe)]}n (2). Two one-dimensional butterfly and cubane-like argento-selenotungstate clusters bridged by dppe ligands were characterized by single crystal X-ray diffraction and the optical limiting properties of polymeric cluster 2 with non-central symmetry were also investigated.The synthetic protocols for one-dimensional polymeric heteroseleno-metallic clusters as demonstration {[Et4N][(μ-Br)(μ 3-WSe4)Ag2(μ-dppe)]}n (1) with the butterfly type and {[Et4N][(μ 3-Br)(μ 3-WSe4)Ag3Cl(μ-dppe)]}n (2) with the cubane-like type are firstly reported, which are constructed by linking up monomeric inorganic cluster with organic bridging ligands.Display Omitted
Keywords: Argento-selenotungstate cluster; One-dimensional polymeric cluster; Synthesis; Crystal structure; Optical limiting property;

Two phenoxy-imine complexes 1d and 2d bearing bulky substituents were synthesized by introducing ethyl or vinyl substituted phenyl to the para position of N-aryl group and characterized by 1H NMR, 13C NMR, and elemental analysis. The X-ray crystallographic analysis revealed a distorted octahedral geometry of complex 2d. When activated by dried MAO, two titanium complexes exhibited good to high activity (up to 4.5 × 106  g mol− 1(Ti) h− 1) for ethylene polymerization. Using these two complexes, ultra-high molecular weight polyethylene (UHMWPE, Mw  > 1,000,000) can be prepared only by changing polymerization time in mild conditions.The synthesis and structural characterization of novel titanium(IV)complexes 2d and 1d with bulkily Schiff base ligands are reported. Complexes 2d and 1d exhibit high catalytic activity and ability to synthesize UHMWPE at mild conditions.Display Omitted
Keywords: Phenoxy-imine titanium(IV) complex; UHMWPE; Bulky substituents; Ethylene polymerization;

Mixed-valence VIV/VV tetrametallate core {V4N2O14} cluster containing tris(hydroxymethyl)aminomethane and acetylacetone by Piotr Zabierowski; Mariusz Radoń; Janusz Szklarzewicz; Wojciech Nitek (72-75).
Reported is a mixed-valence VIV/VV tetrametallate cluster, which is charge neutral and stable in solution. The complex is characterized by single-crystal X-ray diffraction analysis, IR and UV–VIS–NIR absorption spectroscopy, cyclic voltammetry, room temperature magnetic susceptibility measurements and quantum chemical calculations.Display Omitted
Keywords: Polyoxometallates; Vanadium; Mixed-valence; DFT calculations; X-ray crystal structure; Tris(hydroxymethyl)aminomethane;

The mercarbides C(HgX)4 with X  = Cl and acetate which are characterized by a tetrahedral (C4 −Hg2 + 4)4 + core fragment show two absorptions in the UV spectral region at λmax  = 234 nm and 270 nm. They are attributed to (C4 −  → Hg2 +) LMCT transitions. LMCT excitation of C(HgX)4 in solution leads to a photoredox decomposition according to: C(HgX)4  + 2 H2O → CO2  + 4 Hg0  + 4 HX.Display Omitted
Keywords: Photochemistry; Organometallic chemistry; Carbide; Mercury;

Temperature-induced reversible isostructural phase transition in N-isopropylbenzylammonium trifluoromethanesulfonate by Weiling Xiong; Shuquan Zhang; Chengmin Ji; Lina Li; Zhihua Sun; Cheng Song (79-83).
A novel organic molecular phase transition material, N-isopropylbenzylamine trifluoromethanesulfonate (1), which displays the reversible tunable dielectric behavior, has been successfully assembled by the intermolecular hydrogen-bonds. It undergoes a first-order solid-to-solid state phase transition at 189.7 K (T c), being confirmed by thermal analyses including differential scanning calorimetry (DSC), specific heat (Cp) and dielectric measurements. The dielectric constant and dielectric loss of 1 exhibit obvious anomalies and slight tunabilities triggered by heating when the temperature increases approaching to T c. Variable-temperature single crystal X-ray diffraction demonstrates that the origin of its phase transition may be ascribed to the order–disorder transformation of trifluoromethanesulfonate anions, together with the slight twisting motions of the isopropyl groups in N-isopropylbenzylammonium cation. All the findings make us believe that 1 might be a potential phase transition material.Compound 1 undergoes a first-order phase transition which has been confirmed by the variable temperature single-crystal structure analyses, DSC and dielectric measurements.Display Omitted
Keywords: Phase transition; Trifluoromethanesulfonate acid; Dielectric constant; N-isopropylbenzylammonium cation;

Through hydrothermal reactions of d0 metal ions with 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (HL), two new octamolybdate-based hybrids, namely, (H2L)2[Ag2(HL)2(β-Mo8O26)] (1) and [Cu4(HL)4(θ-Mo8O26)] · 5H2O (2), have been prepared and structurally characterized. X-ray single-crystal analyses show that compound 1 consists of discrete H2L cations and infinite one-dimensional (1D) anionic chains [Ag2(HL)2(β-Mo8O26)]2 − constructed by [β-Mo8O26]4 − bridged via dinuclear clusters {Ag2(HL)2}2 +. Compound 2 displays a 2D network generated by 1D cationic tetranuclear copper cluster chains {Cu4(HL)4} n and [θ-Mo8O26]4 − clusters. In addition, luminescent properties of both compounds have been studied.Two new octamolybdate-based hybrids have been prepared and structurally characterized. X-ray single-crystal analyses show that 1 consists of infinite 1D anionic chains constructed by [β-Mo8O26]4– bridged via dinuclear silver clusters. 2 displays a 2D network generated by 1D cationic tetranuclear copper cluster chains and [θ-Mo8O26]4–.Display Omitted
Keywords: Octamolybdate; Hydrothermal synthesis; Hybrid; Tetrazole;

A colorimetric sensor for Fe2 + ion by Chang-Hung Chen; Chien Cho; Chin-Feng Wan; An-Tai Wu (88-91).
A simple Schiff-based receptor 1 was synthesized and investigated its binding properties toward various metal ions in polar solvent (MeOH). Receptor 1 showed a dramatic color change from colorless to black which could easily be detected by the naked-eye upon binding with Fe2 +.Receptor 1 showed a dramatic color change from colorless to black which could easily be detected by the naked-eye upon binding with Fe2 +.Display Omitted
Keywords: Schiff-base; Colorimetric; Chemosensor; Reversibility;

Two coordination polymers, {[Cu2(tbip)2(bie)]∙6H2O} n (1) and {[Cu2(tbip)2(bmib)(H2O)]} n (2) (H2tbip = 5-tert-butyl isophthalate, bie = 1,2-bis(imidazol-1-yl)ethane, bmib = 1,4-bis(2-methylimidazol-1-yl)butane) have been synthesized by hydrothermal methods. Complex 1 is constructed from [Cu2(tbip)2] n layers and further pillared by bie into a 3D (4,6)-connected (42·52·62)(42·56·64·73) network. Complex 2 exhibits a 2-fold interpenetrating 3D pcu framework. Magnetic susceptibility measurements indicate that 1 shows weak ferromagnetic interactions and 2 shows weak antiferromagnetic interactions.Two copper(II) coordination polymers based on 5-tert-butyl isophthalate and two related flexible N-donor ancillary ligands have been synthesized and structurally characterized. Moreover, magnetic properties of both complexes have also been investigated.Display Omitted
Keywords: Copper(II) coordination polymers; 5-Tert-butyl isophthalate; 1,2-Bis(imidazol-1-yl)ethane; 1,4-Bis(2-methylimidazol-1-yl)butane; Magnetic properties;

A new cobalt–thiacalix[4]arene compound [(CH3)4N]2 {[Co4Cl(TC4A)(CH3OH)]4(SIP)4(HCOO)2} (CIAC-111) was synthesized by the solvothermal reaction of CoCl2·6H2O, p-tert-butylthiacalix[4]arene (H4TC4A) and 5-sulfoisophthalic acid sodium salt (NaH2SIP). It is featured with a tetrahedral coordination cage with four Co4-TC4A shuttlecock-like subunits as the vertices and four SIP molecules as the tripod linkers located on the triangular faces. The structure and coordination mode of SIP play a crucial role in the formation of such a cage. The magnetic property of this compound was examined.The introduction of tripodal linker 5-sulfoisophthalic acid to the cobalt/thiacalixarene system led to the formation of one unprecedented calixarene-based tetrahedral coordination cages. The structure and coordination mode of the linker play a crucial role in the formation of such a cage.Display Omitted
Keywords: Cage compounds; Calixarenes; Cobalt; Crystal engineering; Magnetic property;