Inorganic Chemistry Communications (v.14, #2)

Contents List (iii-x).

Two zinc-triazole-biphenyldicarboxylate coordination polymers affording a 3D 4-connected 2-fold interpenetrating diamond net and a 2D 6-connected hxl net by Yanli Chen; Yong Fan; Daojun Zhang; Liangliang Huang; Jinhua Jiang; Ping Zhang; Jianing Xu (343-346).
Two new zinc-triazole-biphenyldicarboxylate frameworks based on secondary building units (SBUs), namely, Zn44-O)(trz)2(4,4′-bpdc)2 ( 1 ) and Zn2(trz)2(2,4′-bpdc) ( 2 ), [Htrz = 1,2,4-triazole, H2bpdc = biphenyldicarboxylate] have been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction analyses, X-ray power diffraction, elemental analyses, infrared absorption spectra, and thermogravimetric analyses. Compound 1 is a 2-fold interpenetrating diamond topology constructed from [Zn44-O)(trz)2]4+ SBUs with tetrahedral [Zn44-O)] core and two trz ligands. Compound 2 is a 2D 6-connected hxl network based on [Zn2(trz)2]2+ SBUs. Additionally, these two compounds show emission properties at room temperature in the solid state.Structural views of two new coordination polymers Zn44-O)(trz)2(4,4′-bpdc)2 (1) and Zn2(trz)2(2,4′-bpdc) (2) based on secondary building units (SBUs), 1 is a 2-fold interpenetrating diamond topology constructed from [Zn44-O)(trz)2]4+ SBUs, and 2 is a 2D 6-connected hxl network based on [Zn2(trz)2]2+ SBUs.Display Omitted► Two new compounds were synthesized under hydrothermal conditions. ► 1 exhibits a 4-connected porous 2-fold interpenetrating diamond network. ► 2 is a 6-connected hxl net. ► The two compounds show emission properties at room temperature in the solid state.
Keywords: Secondary building units; Triazole; Diamond; hxl network;

Synthesis, structure and properties of one 2-D Ag(I) complex based on trinuclear silver(I) cluster and arene-linked bis(pyrazolyl)methane ligand by Shuang Wang; Gang Yuan; Chunyi Sun; Guangsheng Yang; Kuizhan Shao; Xinlong Wang; Yaqian Lan; Zhongmin Su (347-350).
One 2D coordination polymer, [Ag2(L p)1.5(NO3)](NO3) (1) (L p  =  p  − [CH(pz)2]2C6H4,), has been successfully synthesized under solvothermal conditions by the reaction of arene-linked p-bis[bis(1-pyrazolyl)methyl]benzene ligand with AgNO3. Compound 1 presents the first two-dimensional (2D) framework of trinuclear Ag cluster and L p ligand, and exhibits a three-dimensional (3D) supramolecular structure supported by the weak interactions between neighboring sheets. It was characterized by IR, PXRD, single-crystal X-ray diffraction and thermogravimetric analysis. The fluorescence property of compound 1 has also been studied.One novel 2D supramolecular compound based on the arene-linked bis(pyrazolyl)methane ligand and trinuclear Ag cluster has been successfully synthesized under the solvothermal conditions. The fluorescence property of this complex has also been studied.Display Omitted► In this paper, we reported and characterized one 2D supramolecular polymer utilizing arene-linked bis(pyrazolyl)methane ligand and silver cations. ► This complex based on trinuclear Ag cluster provided a new coordination mode of arene-linked bis(pyrazolyl)methane ligand and exhibited the first example of 2D structure in the system of arene-linked bis(pyrazolyl)methane ligand. ► The framework further extended into a three-dimensional (3D) supramolecular structure by weak interaction.
Keywords: Coordination polymer; Solvothermal synthesis; Supramolecular network; Ag(I) complex; Bis(pyrazolyl)methane ligand;

Highly selective fluorescent chemosensor for Fe3+ imaging in living cells by Srung Smanmoo; Weerachai Nasomphan; Pramuan Tangboriboonrat (351-354).
2-Hydroxybenzyl dansyl cadaverine (DNSCH) was designed as a fluorescent chemosensor for Fe3+. DNSCH exhibited significant FL quenching with increasing concentrations of Fe3+. The presence of 15 M equiv of Fe3+ significantly quenched the FL intensity of DNSCH. The binding constant of DNSCH towards Fe3+ was determined and found to be 1.5 ± 0.4 × 10−4  M−1. DNSCH was employed as an intracellular chemosensor for Fe3+.The novel of this work is to synthesize 2-hydroxybenzyl dansyl cadaverine (DNSCH) as a selective fluorescent chemosensor for Fe3+. Of all screened metals, DNSCH exhibited FL quenching upon the addition of Fe3+. DNSCH was found its bio-application as an intracellular chemosensor for Fe3+.Display Omitted► A novel chemosensor based on 2-hydroxybenzyl dansyl cadaverine (DNSCH) is prepared and evaluated for its fluorescence response to heavy metal ions. ► DNSCH exhibits an “off-type” mode with high selectivity in the presence of Fe3+ ion. ► The addition of EDTA recovered the fluorescence of DNSCH·Fe3+ complex offers DNSCH as a reversible chemosensor. ► DNSCH is able to use as an intracellular chemosensor for Fe3+ ion.
Keywords: Fluorescent chemosensor; Fe3+ sensor; Dansyl cadaverine; Fluorescence quenching; Bioimaging;

Urothermal synthesis of a photoluminescent zinc coordination polymer by Zi-Sheng Liu; E. Yang; Yao Kang; Jian Zhang (355-357).
Solvent plays an important role in the self-assembly of metal-organic frameworks (MOFs). It has been demonstrated that the urea derivatives are a new kind of useful solvents, and a new synthetic method denoted as “urothermal synthesis” is emerging. Presented here are the urothermal synthesis, structure and photoluminescent property of an interesting coordination polymer {Zn3[(sip)2(tmdpy)2(e-urea)4(H2O)2](e-urea)2}n (1; sip = 5-sulfoisophthalate; tmdpy = 1.3-di(4-pyridyl)propane; and e-urea = 2-imidazolidinone) with ladder-like structure.An interesting coordination polymer with ladder-like structure and photoluminescent property is urothermally synthesized by using ethyleneurea as the solvent.Display Omitted► Solvent plays an important role in the self-assembly of metal-organic frameworks (MOFs). ► Recently, the urea derivatives have been demonstrated to be a new kind of useful solvents, and a new synthetic method denoted as “urothermal synthesis” is emerging. ► Presented here is the urothermal synthesis, structure and photoluminescent property of an interesting coordination polymer {Zn3[(sip)2(tmdpy)2(e-urea)4(H2O)2](e-urea)2}n (1; sip = 5-sulfoisophthalate; tmdpy = 1,3-di(4-pyridyl)propane; e-urea = 2-imidazolidinone) with ladder-like structure.
Keywords: Zinc; Urothermal; 2-imidazolidinone; Crystal structure; Photoluminescence;

Isomeric photoluminescent lead(II) coordination polymers based on designed pyridinecarboxylate ligands by Xin Zhang; Jiankai Cheng; Feng Chen; Mingling Sun; Yuangen Yao (358-361).
The hydrothermal reaction of Pb(OAC)2·3H2O with the flexible multidentate ligand 5-(pyridin-2-ylmethoxy)-isophthalic acid (H2L1) or 5-(pyridin-4-ylmethoxy)-isophthalic acid (H2L2), respectively, afforded two new metal–organic frameworks, [Pb2L12]n (1) and [Pb2L22]n (2). The single-crystal X-ray analysis shows that 1 is a two-dimensional (2D) layered structure, whereas 2 is a three-dimensional (3D) pillar-layered network. Both of them exhibit strong yellow photoluminescence upon excitation 366 nm at room temperature.Presented here are two new isomeric photoluminescent Pb(II) coordination polymers, [Pb2L12]n (1, L1 = 5-(pyridin-2-ylmethoxy)-isophthalate) and [Pb2L22]n (2, L2 = 5-(pyridin-4-ylmethoxy)-isophthalate), which possess distinct topological structures and photoluminescent properties.Display Omitted► In this work, we designed and synthesized two new pyridinecarboxylic aids, 5-(pyridin-2-ylmethoxy)-isophthalic acid (H2L1) and 5-(pyridin-4-ylmethoxy)-isophthalic acid (H2L2) (Scheme 1). ► There exists a flexible CH2-O spacer between the pyridine and phenyl ring in both structures of H2L1 and H2L2, which will enable them adopt suitable configurations according to the geometric requirements of different metal ions during the self-assembly process. ► Successfully, the hydrothermal reactions of Pb(OAC)2•3H2O with H2L1 and H2L2, respectively, lead to two novel lead (II) compounds, [Pb2(L1)2]n (1) and [Pb2(L2)2]n (2).
Keywords: Flexible ligand; Isomers; Layered structure; Photoluminescence;

Synthesis, structure, and magnetic properties of new pyridonate–pivalate nickel(II) complex, [Ni11(OH)2(mhp)8(Piv)10(HCO2)2(H2O)2(Hmhp)2(HPiv)2] (mhp = 6-methyl-2-pyridonate), containing formate bridges by Marina E. Nikiforova; Mikhail A. Kiskin; Artem S. Bogomyakov; Grygory G. Aleksandrov; Aleksei A. Sidorov; Vladimir S. Mironov; Igor L. Eremenko (362-365).
The undecanuclear complex [Ni11(OH)2(mhp)8(Piv)10(HCO2)2(H2O)2(Hmhp)2(HPiv)2] (2, where Piv is the anion of pivalic acid) containing 6-methyl-2-pyridonate, pivalate and formate anions have been obtained as a result of interaction of trimethylacetate (or pivalate) nickel(II) complex [Ni9(OH)6(Piv)12(HPiv)4] with 2-hydroxy-6-methylpyridine in dimethoxyethane, containing about 0.50% of methyl formate. The structure of 2 is determined using X-ray diffraction analysis and its magnetic susceptibility is measured between 2 and 300 K. It is shown that complicated low-temperature magnetic behavior of 2 is due to combined influence of competing ferro- and antiferromagnetic interactions, zero-field splitting effect and anisotropic exchange interactions in the Ni11 clusters.New pyridonate–pivalate nickel(II) complex, [Ni11(OH)2(mhp)8(Piv)10(HCO2)2(H2O)2(Hmhp)2(HPiv)2] containing formate bridges has been synthesized.Display Omitted► Mixed ligand complex. ► Molecular undecanuclear complex of nickel(II). ► Ferro- and antiferromagnetic interactions, zero-field splitting effect.
Keywords: Polynuclear nickel(II) complex; Pyridonate ligands; Carboxylate ligands; X-ray diffraction analysis; Magnetic properties;

A tetrapodal ligand, tetrakis[3-(carboxyphenyl)oxamethyl] methane acid (H4L), and its cadmium complex [Cd2L(H2O)2]n (1) were synthesized and structurally characterized. Complex 1 displays a three-dimensional (3,6)-connected anatase topology with the Schläfli symbol (42.6)2(44.62.88.10). At room temperature, complex 1 exhibits a strong emission at 396 nm upon excitation at 320 nm.Self-assembly of a tetrapodal ligand and cadmium acetate produces a 3D coordination polymer with an anatase topology, which shows strong blue luminescence.Display Omitted► A cadmium complex with tetrapodal ligand has been synthesized. ► Topological analysis of the cadimium complex indicates it has an anatase topology. ► The photoluminescent property of the title complex has also been investigated.
Keywords: Cadmium (II) complex; Tetrapodal ligand; Anatase topology; Luminescence;

A zipper-like double chain coordination polymer constructed from a novel pseudo-macrocyclic binuclear Cu(II) complex by Cai-Xia Ding; Jia Ni; Chang-Hua He; Fan-Hua Zeng; Wei-Hong Zhu; Yong-Shu Xie (370-373).
A novel coordination polymer [Cu2(HL)(CH3OH)(ClO4)]n(ClO4)n (1) has been synthesized from a multihydoxy Schiff base ligand, 1,3-bis(salicylidene iminoethylamino)-2-propanol (H3L). Single crystal X-ray diffraction analyses reveal that the coordination polymer is comprised of binuclear units, wherein the copper centers are bridged by a single alkoxo group, with a large bridging angle of 135.06°. By the linkage of an intramolecular hydrogen bond, an interesting pseudo-macrocyclic structure is formed. The binuclear moieties are assembled into a 1-D chain by the linkage of axially coordinated ClO4 anions, and the 1-D chains are further connected via intermolecular C-H⋅⋅⋅π stacking interactions, affording a zipper-like double chain supramolecular structure. Variable-temperature magnetic data measurements and analyses show the existence of strong antiferromagnetic interaction between the copper centers within the binuclear unit, mediated by the single alkoxo bridge with a − 2J value of 545 cm− 1.A novel coordination polymer [Cu2(HL)(CH3OH)(ClO4)]n(ClO4)n (1) has been synthesized from a multihydoxy Schiff base ligand, 1,3-bis(salicylidene iminoethylamino)-2-propanol (H3L). 1 has a zipper-like double chain supramolecular structure formed by weak axial coordination and intermolecular C-H⋅⋅⋅π stacking interactions.Display Omitted► Pseudo-macrocyclic structure is formed by the linkage of an intramolecular H-bond. ► Complex structure is modulated by the ligand rigidity. ► An interesting supramolecular zipper-like double chain structure is formed. ► Strong antiferromagnetic coupling is mediated by a single alkoxo-bridge.
Keywords: Crystal structures; Copper(II) complexes; magnetic properties; Alkoxo bridges; Double chains;

Self-assembled tetranuclear metallacyclic chair using orthogonal tritopic acceptors, angular ditopic donors, and bischelating bridging motifs by Bhaskaran Shankar; Palanisamy Rajakannu; Surendra Kumar; Deepak Gupta; Tharanikkarasu Kannan; Malaichamy Sathiyendiran (374-376).
Self-assembled neutral tetrarhenium molecular chair was prepared using orthogonal tritopic acceptors, angular ditopic N-donors (~ 80°), and linear bis-chelating bridging donors in a one-step process.Self-assembled neutral metallacyclic chair architecture was prepared using orthogonal tritopic acceptors, angular ditopic N-donors (~ 80°), and planar bis-chelating bridging ligands in a one step process. Angular ditopic ligand and metallacycle 1 were characterized with EA, IR, 1H−NMR, UV−Visible and fluorescence spectroscopic methods.Display Omitted► Neutral Re(I)-based metallacyclic chair by self-assembly in a one-step process. ► Solvothermal process for preparation of tetrarhenium molecular chair. ► New bonding combinations i.e., orthogonal tritopic acceptors, angular ditopic N-donors (~ 80°), and bischelating ligands.
Keywords: Metallacycle; Nitrogen donor; Rhenium carbonyl; Self-assembly; Supramolecular chemistry;

Synthesis of the tris-cyclometalated complex fac-[Rh(ptpy)3] and X-ray crystal structure of [Rh(acac)(ptpy)2] by Hans-Christian Böttcher; Marion Graf; Karlheinz Sünkel; Beatrice Salert; Hartmut Krüger (377-379).
New convenient syntheses of the cyclometalated complexes [Rh(acac)(ptpy)2] (3, ptpy = 2-(p-tolyl)pyridinato) and fac-[Rh(ptpy)3] (4) are described. The compounds were prepared in a kind of one-pot synthesis starting from in situ prepared [Rh(acac)(coe)2] (2) (coe =  cis-cyclooctene) followed by reaction with Hptpy in refluxing toluene. Under these conditions oxidative addition occurred and the new complex 3 was obtained in good yields. Compound 4 was prepared in good yields by reaction of 3 with Hptpy in excess. The complex 3 crystallized from dichloromethane/iso-hexane in the space group P  − 1 and its molecular structure was confirmed by a single-crystal X-ray diffraction study. The absorption and emission spectra exhibit the new compounds as red-emitting phosphorescent complexes.New convenient syntheses of [Rh(acac)(ptpy)2] (3) and fac-[Rh(ptpy)3] (4) (ptpy = 2-(p-tolyl)pyridinato), respectively, and the crystallographic characterization of 3 are reported. The absorption and emission spectra exhibit the new complexes as red-emitting phosphorescent compounds.Display Omitted► Syntheses of cyclometalated rhodium complexes with the 2-(p-tolyl)pyridinato) ligand. ► Crystallographic characterization of [Rh(acac)(ptpy)2]. ► The new complexes are red-emitting phosphorescent compounds.
Keywords: Rhodium complexes; Cyclometalation; Crystal structure; Phosphorescence;

Ionothermal syntheses and crystal structures of two cobalt(II)–carboxylate compounds with different topology by Yu-Ling Wang; Na Zhang; Qing-Yan Liu; Xin Yang; Hong Bai; Lin-Yan Duan; Hong-Yu Liu (380-383).
Two cobalt–carboxylate compounds, namely, {[PMIM]2[Co2(BTC)2(H2O)2]}n (1) (PMIM = 1-propyl-3-methylimidazolium and H3BTC = 1,3,5-benzenetricarboxylic acid) and [Co3(BDC)3(IM)2]n (2) (H2BDC = 1,4-benzenedicarboxylic acid and IM = imidazole) have been synthesized under ionothermal reactions. Compound 1 has a 3D anionic framework with (4.62)2(42.610.83) topology based on dinuclear cobalt(II) as a secondary building unit. The imidazolium cation [PMIM]+ of the ionic liquid acting as extraframework charge-balancing species occupies the channels of the 3D anionic framework. Complex 2 features a 3D neutral framework with (412.63) topology constructed of unusual linear trinuclear cobalt(II) as a secondary building unit. The rich ionic environments of the ionic liquid may be particularly helpful in the formation of the frameworks of 1 and 2. The roles of the ionic liquid in ionothermal syntheses and crystallizations of compounds are briefly discussed.Two cobalt(II)–carboxylate compounds, {[PMIM]2[Co2(BTC)2(H2O)2]}n (1) and [Co3(BDC)3(IM)2]n (2), have been synthesized under ionothermal reactions. Compound 1 has a 3D anionic framework with (4.62)2(42.610.83) topology based on dinuclear cobalt unit with charge-compensating agent of [PMIM]+. Complex 2 features a 3D neutral framework with (412.63) topology constructed of unusual linear trinuclear cobalt unit.Display Omitted►Cobalt(II)–carboxylate compounds. ►Ionothermal synthesized. ►3D anionic framework with (4.62)2(42.610.83) topology based on dinuclear cobalt unit. ►3D neutral framework with (412.63) topology constructed of unusual linear trinuclear cobalt unit.
Keywords: Ionothermal synthesis; Cobalt compounds; Crystal structure; Topology;

Two large ionic crystals: Both their anions and cations constructed by Anderson-type POM-supported transition metal complex by Rui–Kang Tan; Shu–Xia Liu; Wei Zhang; Shu–Jun Li; Yuan–Yuan Zhang (384-388).
Two large ionic crystals, [{Cu(C12N2H8)(H2O)3}2{Al(OH)6Mo6O18}][{Cu2(C2O4)(C12N2H8)2} {Al(OH)6Mo6O18}]·10H2O (1) ≡ [1c][1a]·10H2O ≡  1 and [{Cu(C12N2H8)(H2O)3}2{Cr(OH)6Mo6O18}][{Cu2(C2O4)(C12N2H8)2} {Cr(OH)6Mo6O18}]·12H2O (2) ≡ [2c][2a]·12H2O ≡  2, whose anions and cations constructed by Anderson–type POM–supported transition metal complex, have been isolated by conventional solution method, and characterized by elemental, IR, thermogravimetric, X-ray powder diffraction, EPR, magnetic and single-crystal X-ray diffraction analyses. Compounds 1 and 2 are isomorphic and consist of one-dimensional anion chains, which are constructed by alternating Anderson-type polyoxoanions and dinuclear copper complexes. 1D anions chains, 1c (2c) cations and lattice waters lead to their three-dimensional structures through hydrogen bonds and π–π interactions. The EPR studies and magnetic studies elucidate the electronic properties of the metal ions (Cu2+ or Cu2+/Cr3+), and the results are in good agreement with the structural feature of these compounds.Two large ionic crystals, [{Cu(C12N2H8)(H2O)3}2{Al(OH)6Mo6O18}][{Cu2(C2O4)(C12N2H8)2} {Al(OH)6Mo6O18}]·10H2O (1) ≡ [1c][1a]·10H2O ≡  1 and [{Cu(C12N2H8)(H2O)3}2{Cr(OH)6Mo6O18}][{Cu2(C2O4)(C12N2H8)2} {Cr(OH)6Mo6O18}]·12H2O (2) ≡ [2c][2a]·12H2O ≡  2, whose anions and cations constructed by Anderson-type POM-supported transition metal complex, have been isolated by conventional solution method, and characterized by elemental, IR, thermogravimetric, X-ray powder diffraction, EPR, magnetic and single-crystal X-ray diffraction analyses.Display Omitted► Two large ionic crystals exhibit strong antiferromagnetic coupling. ► Anions and cations are constructed by Anderson-type POM-supported transition metal complex. ► Anderson-type polyoxoanions supported oxalate-bridged dinuclear copper complex act as anions.
Keywords: Ionic crystals; Polyoxometalates; Anderson-type; Transition metal complex;

Dicopper(II) complexes of chiral C 2 -symmetric diamino-bis(2-methylpyridyl) and diamino-bis(2-methylbenzimidazolyl) ligands by Viridiana Pérez; Iván Monsalvo; Patricia Demare; Virginia Gómez-Vidales; Ignacio Regla; Ivan Castillo (389-391).
Reaction of the chiral ligands (1S,4S)-2,5-bis(6-methylpyridyl)-diazabicyclo[2.2.1]heptane (L 1 ), and (1S,4S)-2,5-bis(2-methylbenzimidazolyl)-diazabicyclo[2.2.1]heptane (L 2 ) with copper(II) acetate results in the hydroxo-bridged dicopper complexes [(L 1 )Cu2(μ-OH)(H2O)(OAc)2Cl] (1-Cl·H2O), and [(L 2 )Cu(μ-OH)(H2O)(MeOH)(OAc)2]OAc (2 .H2O,MeOH). Both chiral complexes were characterized spectroscopically, as well as in the solid state by X-ray crystallography.► C 2 -symmetric diazabicycle allows preparation of tetradentate ligands. ► Chiral ligands with diamino-bis(pyridine) and diamino-bis(benzimidazole) N4 donor sets were obtained. ► Reactions with copper(II) acetate result in chiral μ-hydroxo-bridged dicopper complexes.Chiral tetradentate ligands with diamino-bis(2-methylpyridyl) and diamino-bis(2-methylbenzimidazolyl) donor sets react with copper(II) acetate affording chiral bimetallic complexes.Display Omitted
Keywords: Copper; Chiral ligands; Pyridine; Benzimidazole;

Synthesis and reactivity of acetylacetone with amine ligands in fac-Re(OH2)3(CO)3 + complexes by Paul D. Benny; Tanushree Ganguly; Lyndel Raiford; Glenn A. Fugate; Brendan Twamley (392-395).
The fac-Re(OH2)3(CO)3 + moiety was investigated with a known bidentate ligand, acetylactone (acac) and amine based ligands in a 2 + 1 and tridentate approach. In the 2 + 1 approach, the fac-Re(CO)3(acac)(OH2) was reacted with ethylamine to yield the monomer version fac-Re(CO)3(acac)(NH2Et), 1. Based on the Schiff base condensation of a ketone and a primary amine, a tridentate ligand approach for fac-Re(OH2)3(CO)3 + utilizing the reactivity of acac and diamine ligands (1,2 ethylene, 1,3 propylene, 1,4 butylene) was explored in a didactic manner: 1) an in situ ligand synthesis approach reacting fac-Re(CO)3(acac)(OH2) with the diamine (2 + 2 = 3) or 2) direct complexation of fac-Re(OH2)3(CO)3 + with the prepared ligand. The results observed with rhenium complexes were characterized by standard chemical analysis and X-ray analysis.The fac-Re(CO)3 + moiety was investigated with a known bidentate ligand, acetylacetone (acac) to generate fac-Re(CO)3(acac)(OH2) followed by the introduction of amine based ligands in a 2 + 1 and tridentate approach.Display Omitted► Denticity of amine based ligands impacts the type of complex observed. ► Re(CO)3(acac) with amine donors can form 2 + 1 or tridentate complexes. ► Amines coordination vs. Schiff base condensation.
Keywords: Rhenium; acac; Complexes; Carbonyl;

Two sets of 3d–4f complexes [(NiL)nRE] (n = 1, 2; RE = La and Ce; H2L = N,N′-bis(3-ethoxysalicylidene)ethylenediamine) were obtained by reacting NiL with RE(NO3)3 in the ratios of 1/1 and 2/1, respectively. With the NiL/RE ratio changing from 1/1 to 2/1, not only the crystal structures were changed from discrete dinuclear complexes [(NiL)RE] to sandwich-like trinuclear complexes [(NiL)2RE], but also the biological activities were greatly influenced. The trinuclear complexes [(NiL)2RE] exhibited higher antimicrobial activities than the corresponding dinuclear counterpart [(NiL)RE].The trinuclear (NiL)2RE complexes or dinuclear (NiL)RE complexes (Ln = La and Ce) could be obtained when the ratio of NiL to RE was adjusted to 2:1 and 1:1, respectively. The trinuclear (NiL)2RE complex sets have higher antimicrobial activities than the corresponding dinuclear counterpart (NiL)RE.Display Omitted► Two sets of 3d-4f complexes were obtained by adjusting the ratio of raw materials. ► The biological activities were greatly influenced by the structure change. ► Sandwich-like trinuclear complexes exhibited higher antimicrobial activities.
Keywords: Salen-type Schiff base ligand; 3d–4f complexes; Crystal structure; Biological activities;

Paramagnetic Ru(III) complexes of tridentate ligands: Characterization of useful intermediates for heteroleptic Ru(II) complexes by Marie-Pierre Santoni; Amlan K. Pal; Garry S. Hanan; Anna Proust; Bernold Hasenknopf (399-402).
Paramagnetic Cl3Ru(L) complexes of tridentate ligands (2a: L =  1a  = 4′-(p-bromophenyl)-2,2′:6′,2″-terpyridine; 2b: L =  1b  = 6-(p-bromophenyl)-2,4-dipyrid-2-yl-1,3,5-triazine) were synthesized in a high-yield method with facile isolation of these useful synthons. The complexes were isolated in high purity and were characterized by several methods, including standard techniques such as 1H NMR and electrospray ionization mass spectrometry. The 1H NMR of the complexes displayed peaks from + 10 to − 37 ppm, with the protons ortho to the nitrogen atoms coordinated to the paramagnetic centre being shifted the most (2a: H6,6″  = − 35.3 ppm; 2b: H6,6″  = − 26.1 ppm), while the protons on the non-bonding phenyl rings were relatively unchanged with respect to their uncomplexed ligands. The electronic absorption spectra of the complexes displayed both 1LMCT bands (Cl-to-Ru, 2a: λmax = 405 nm; 2b: λmax = 420 nm) and 1MLCT (Ru-to-L, 2a: λmax = 486 nm; 2b: λmax = 567 nm) bands. Due to the ease of purification and high yields, the use of complex 3, first introduced by Chatt, is the method of choice to form Cl3Ru(L) complexes of tridentate ligands.Paramagnetic Cl3Ru(L) complexes of the tridentate ligands 2,2′:6′,2″-terpyridine and 2,4-dipyrid-2-yl-1,3,5-triazine were synthesized in high purity and were characterized by 1H NMR, with peaks ranging from + 10 to − 37 ppm.Display Omitted► Paramagnetic Cl3Ru(L) complexes of tridentate ligands were isolated in high purity and were characterized by several methods. ► The 1H NMR of the complexes displayed peaks from + 10 to − 37 ppm. ► The electronic absorption spectra of the complexes displayed both 1LMCT bands and 1MLCT bands.

Solvothermal reactions of CdSO4·8/3H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and HCl in H2O, MeOH or EtOH afforded three coordination complexes [Cd5Cl2(μ-Cl)43-Cl)2(η,η,η-μ3-SO4)2(H2O)2(Htitmb)2] n (1), [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)2(titmb)2] n (2) and [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] (3), respectively. All the compounds were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 has a 1D chain in which each centrosymmetric double butterfly-shaped [Cd5Cl2(μ-Cl)43-Cl)2(H2O)2] unit interlinks with its equivalent ones via two couples of η,η,η-μ3-SO4 anions and two pairs of the Htitmb ligands. Compound 2 consists of one centrosymmetric [Cd5Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)4(titmb)2] unit that interconnects with equivalent ones via sharing Cd3 and its symmetry-related ones, forming a 1D zigzag chain. Compound 3 consists of a [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2] unit linked by a pair of titmb ligands. The results may provide some insight into solvent effects on the formation of different coordination compounds from the same components.Reactions of CdSO4·8/3H2O with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and HCl in 1:1:1 molar ratio in H2O, MeOH or EtOH under solvothermal conditions gave rise to three different coordination complexes [Cd5Cl2(μ-Cl)43-Cl)2(η,η,η-μ3-SO4)2(H2O)2(Htitmb)2]n, [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2(MeOH)2(titmb)2] n and [Cd4Cl2(μ-Cl)2(η,η,η-μ3-SO4)2], respectively. The three complexes were structurally characterized by elemental analysis, IR, thermogravimetric analysis and X-ray crystallography.Display Omitted► Reactions of CdSO4, titmb and HCl in three solvents gave three complexes. ► Compound 1 is a 1D chain polymer. ► Compound 2 is a 1D zigzag chain polymer. ► Compound 3 is a tetranuclear Cd compound. ► Solvent effects on forming different complexes from the same components were found.
Keywords: Solvothermal reactions; Crystal structures; Solvent effects; 1,3,5-Tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene; Cadmium;

A novel metal–organic framework with bifunctional tetrazolate-5-carboxylate ligand: Crystal structure and luminescent properties by Yan Li; Xin-Hua Zhong; Fa-Kun Zheng; Mei-Feng Wu; Zhi-Fa Liu; Guo-Cong Guo (407-410).
Hydrothermal reaction of NaN3, Na(4-cba) (4-Hcba = 4-cyanobenzoic acid) and ZnBr2 afforded a novel 3D Zn(II) coordination polymer [Zn2(4-tzba)2(H2O)]n 1 (4-H2tzba = 4-(5H-tetrazol)benzoic acid). In situ [2 + 3] cycloaddition reaction of nitrile and azide in the presence of ZnBr2 yielded tetrazolate-5-carboxylate 4-tzba2− ligand. Compound 1 displays an unprecedented four-connected topological network with 1D hexagonal channels constructed from trigonal rings [Zn3(4-tzba)6]. The solid-state photoluminescent studies revealed that 1 exhibits a strong blue emission mainly originating from 4-tzba2− ligand-centered charge transition.A novel 3D Zn(II) coordination polymer based on bifunctional tetrazolate-5-carboxylate ligand features an unprecedented four-connected topological network with hexagonal channels constructed from trigonal rings and displays a strong blue emission.Display Omitted► A novel 3D coordination polymer with 1D hexagonal channels constructed from trigonal rings. ► An unprecedented four-connected network with a (42.64)(62.84)(4.63.82) topology. ► A good candidate for efficient blue emission materials.
Keywords: Metal–organic frameworks; Tetrazolate-5-carboxylate ligand; Trigonal ring; Tubular structure; Luminescent properties;

Homo-chiral self-assemblies and magnetic studies of M(II)-2,2′-bipyridine-4,4′-dicarboxylate coordination polymers by Pei-Zhou Li; Naoki Muramatsu; Goro Maruta; Sadamu Takeda; Qiang Xu (411-414).
Homochiral self-assembly is a challenging task, especially from achiral components without any chiral auxiliary. Based on rational selection of achiral organic ligand, two kinds of chiral coordination polymers, {Mn(o 1 ,o 2 -μ-bpdc)(H2O)2}n (1) and {Ni(o 1 ,o 1 -μ-bpdc)(H2O)2}n (2) (bpdc = 2,2′-bipyridine-4,4′-dicarboxylate), have been successfully synthesized by hydrothermal reaction. The X-ray single crystal determination and the structural insight indicate that the coordination behaviors of both bpdc ligands and metal ions between the two kinds of coordination polymers are distinct. Temperature dependent magnetic studies reveal that Mn(II) ions in 1 show antimagnetic interactions, while Ni(II) ions in 2 show weakly ferromagnetic interactions.Two kinds of chiral coordination polymers were synthesized from achiral components through homo-chiral self-assembly. The systematical structural investigation indicated that coordination behaviors of both the ligands and metal ions were distinct. The magnetic studies reveal that one shows antimagnetic behaviors between the ions, while the other shows weakly ferromagnetic behaviors between the ions.Display Omitted► 2,2’-bipyridine-4,4’-dicarboxylate (bpdc) as a functional organic ligand. ► Two chiral coordination polymers formed by the same achiral organic ligand. ► Two chiral coordination polymers in distinct coordination and magnetic behaviors.
Keywords: Chiral coordination polymer; Manganese complex; Nickel complex; 2,2′-Bipyridine-4,4′-dicarboxylate; Magnetic property;

A novel inorganic–organic hybrid 1D chain built by double banana-shaped tungstoarsenates {Co(Hen)[Co6As3W24O94(H2O)2]}2 28− by Pengtao Ma; Lijuan Chen; Junwei Zhao; Wei Wang; Jingping Wang; Jingyang Niu (415-418).
A novel inorganic–organic hybrid 1D chain tungstoarsenate (H2en)4H20{Co(Hen) [Co6As3W24O94(H2O)2]}2·15H2O (en = ethylenediamine) (1) has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum and single-crystal X-ray diffraction. 1 contains a double banana-shaped tungstoarsenate anion {Co(Hen)[Co6As3W24O94(H2O)2]}2 28−, which is established by two banana-shaped {Co(Hen)[Co6As3W24O94(H2O)2]}14− subunits linked together by a W–O–Co bridge. More importantly, adjacent double banana-shaped polyoxoanions {Co(Hen)[Co6As3W24O94(H2O)2]}2 28− are interconnected by W–O–Co linkers leading to the 1D chain architecture, to our knowledge, which represents the first inorganic–organic hybrid 1D chain constructed from double banana-shaped polyoxoanions. Magnetic measurements indicate that there are the antiferromagnetic interactions within the cobalt centers.The first inorganic–organic hybrid 1D chain tungstoarsenate (H2en)4H20{Co(Hen)[Co6As3W24O94(H2O)2]}2·15H2O built by double banana-shaped units {Co(Hen)[Co6As3W24O94(H2O)2]}2 28− has been hydrothermally synthesized and structurally characterized.Display Omitted► A new inorganic–organic hybrid tungstoarsenate contains double banana-shaped anions. ► The hybrid represents the first 1D chain based double banana-shaped polyoxoanions. ► The [Co(Hen)]3+ cation displays an uncommon end-on coordination motif in POM field. ► Antiferromagnetic exchange interactions exist in trinuclear CoII clusters.
Keywords: Polyoxometalate; Tungstoarsenate; Hydrothermal synthesis; Magnetism;

Cobalt hydroxysalt exists in Co(OH)(NO3), Co2(OH)3(NO3), Co3(OH)4(NO3)2 and Co7(OH)12(NO3)2 compositions. Co2(OH)3(NO3) has been prepared by varying the experimental conditions. The X-ray powder diffraction patterns of Co2(OH)3(NO3) obtained by different methods exhibit significant changes in their peak positions and the relative intensities. Careful analysis of the X-ray powder diffraction patterns of Co2(OH)3(NO3) samples reveals that it can crystallize in different polytypic modifications. The thermal decomposition studies show that the Co2(OH)3(NO3) of 3R2 polytype has better structural stability compared to Co2(OH)3(NO3) of 1H polytype.Co2(OH)3(NO3)-I and Co2(OH)3(NO3)-II has been prepared by two different methods and they crystallizes in 3R2 and 1H polytypic modifications. The thermal decomposition studies show that Co2(OH)3(NO3)-I of 3R2 polytype is structurally more stable compared to Co2(OH)3(NO3)-II of 1H polytype.Display Omitted► Co2(OH)3(NO3) has been prepared by varying the experimental conditions. ► The X-ray powder diffraction patterns of Co2(OH)3(NO3) obtained by different methods exhibit significant changes in their peak positions. ► X-ray powder diffraction pattern analyses of Co2(OH)3 (NO3) samples reveal that they crystallize in 3R2 and 1H polytypes. ► Co2(OH)3(NO3)-3R2 polytype has better thermal stability compared to Co2(OH)3(NO3) of 1H polytype.
Keywords: Layered hydroxysalts; Chemical synthesis; Urea hydrolysis; Stacking sequence; Polytypism; Thermal stability;

Observation of induced CD on CdSe nanoparticles from chiral Schiff base Ni(II), Cu(II), Zn(II) complexes by Yoshikazu Aritake; Taku Nakayama; Hitoe Nishizuru; Takashiro Akitsu (423-425).
We prepared supramolecular systems composed of extended chiral Schiff base Ni(II), Cu(II), and Zn(II) complexes having azo-groups, denoted as complexes 13, respectively, and CdSe nanoparticles with various particle sizes which exhibited the shift of absorption and fluorescence spectra. We observed and discussed induced CD bands on CdSe nanoparticles from 1 to 3 (denoted as systems 1–3+ CdSe). Absence of shifts in IR spectra suggested that complexes 13 did not contact to the surface of CdSe nanoparticles directly. Absence of cis-trans photoisomerization of complexes 13 suggested closely contact of 13 near the surface of CdSe nanoparticles. Decrease of the intensity of the CD band at 410 nm for each size of CdSe nanoparticles suggested new mechanism of induced CD bands for the mixed solution.We prepared supramolecular chiral systems composed of extended chiral Schiff base Ni(II), Cu(II), and Zn(II) complexes with azo-groups and CdSe nanoparticles exhibiting various particle sizes absorption and fluorescence spectra, and we observed induced CD as decrease of intensity of at 410 nm.Display Omitted► Induced CD on CdSe nanoparticles from chiral Schiff base Ni(II) complex. ► Induced CD on CdSe nanoparticles from chiral Schiff base Cu(II) complex. ► Induced CD on CdSe nanoparticles from chiral Schiff base Zn(II) complex.
Keywords: Induced CD; CdSe; Nanoparticle; Schiff base; Chirality;

Transformations of acetone in reactions with carboxylate complexes of palladium by Inessa A. Efimenko; Roman E. Podobedov; Oleg N. Shishilov; Yaroslavna N. Rezinkova; Andrei V. Churakov; Lyudmila G. Kuzmina; Irina A. Garbuzova; Boris V. Lokshin (426-428).
Interaction of palladium carboxylates [Pd(RCO2)2] n with acetone was studied and two new types of palladium polynuclear compounds containing acetonyl and carboxylate groups were isolated. The compounds of the first type are resented by Pd4(μ-CF3CO2)4(μ,k 2-CH2C(O)CH3)23-CH2C(OH)CH2)2·2CH3C(O)CH3. This complex has been characterized by the X-ray diffraction analysis. The compound has been shown to contain bridging enolate-anions and η3-coordinated 2-hydroxoallyl ligands. Both ligands represent the result of acetone transformations. The compound is the first transition metal complex simultaneously containing coordinated acetonyl and η3-coordinated 2-hydroxoallyl. The compounds of the second type represent polymeric complexes of the common formula [Pd2(μ-RCO2)2(μ,k 2 -CH2C(O)CH3)2] n (R = CF3, CCl3) containing only bridging enolate-anions. The obtained result shows that, in the presence of strong carboxylic acids, acetone acts as a high-reactive moiety towards palladium carboxylates.Interaction of palladium carboxylates [Pd(RCO2)2] n with acetone was studied and two new types of palladium polynuclear compounds containing acetonyl and carboxylate groups were obtained. The complex Pd4(μ-CF3CO2)4(μ,k 2-CH2C(O)CH3)23-CH2C(OH)CH2)2 was characterized by X-ray analysis and shown to contain η3-coordinated 2-hydroxoallyl ligand which is a result of acetone transformation.Display Omitted►Palladium carboxylates [Pd(RCO2)2] n reveal high reactivity towards acetone. ►The reactivity depends on the presence of strong carboxylic acid. ►Acetone transforms into coordinated enolate-anions and hydroxoallyls. ►The first carboxylate-enolate platinum metal complex was characterized by X-ray analysis.
Keywords: Palladium; Carboxylate; Transformation of acetone; Acetonyl; Hydroxoallyl;

Tetrameric entity resulting from two distinct dinuclear uranyl-centered motifs bridged through μ 2-OH and pyridazine-3,6-dicarboxylate by Natacha Henry; Michel Lagrenée; Thierry Loiseau; Nicolas Clavier; Nicolas Dacheux; Francis Abraham (429-432).
The crystal structure of (UO2)4(pdzdc)3(OH)2(H2O)5·11H2O (pdzdc  = pyridazine-3,6-dicarboxylate) consists of two distinct dinuclear motifs [(UO2)2N4O11] and [(UO2)2N2O10] with eight-fold and seven-fold coordinations for the uranium centers, respectively. The uranium atoms having the same environment are bridged through a μ 2-hydroxo group to each other. The dimeric units are connected to each other through a carboxylate arm from a pdzdc molecule to generate tetranuclear building blocks, which are further assembled into a three-dimensional network by hydrogen bonding. Preliminary investigation of fluorescence property of the complex is presented as well as Raman and Infrared spectroscopies.Reaction of pyridazine-3,6-dicarboxylate with uranyl cation gives rise to the formation of a tetranuclear unit containing two sets of two uranyl centers linked to each other through one carboxylate arm of the organic ligand.Display Omitted► Reactivity of benzene dicarboxylate containing azine group with uranium(VI). ► Tetranuclear motifs from two sets of dinuclear units. ► Complementarities with luminescence, infrared and Raman spectroscopy.
Keywords: Uranyl; Pyridazine-3,6-dicarboxylate; Single-crystal; X-ray diffraction; Luminescence; Raman; Infrared;

A new 3D pillared framework has been obtained through self-assembly of 4,4′-biphenyldicarboxylic acid (4,4′-H2BPDC) and Pb(NO3)2 under solvothermal reaction and characterized by TGA, IR spectroscopy, element analyses, and X-ray single crystal diffraction. The X-ray structure analysis reveals that the oxygen atoms of the carboxylate groups link the Pb(II) to form metal-carboxylate layers, and 4,4′-BPDC ligands act as pillars to connect adjacent layers into a novel 3D pillared framework, where the BPDC displayed a rare μ 6 coordination mode of each BPDC linking with six Pb(II) ions. Furthermore, the highly thermally stable compound 1 exhibits blue photoluminescence at room temperature in the solid state.A novel metal-organic polymer 1, [Pb(BPDC)] possesses parallel 2D infinite Pb-carboxylate layers bridged by carboxylate oxygen atoms. The 2D layers are further linked by the rigid 4,4′-BPDC ligands into a 3D pillared framework.Display Omitted
Keywords: Pb(II); 4,4′-biphenyldicarboxylic acid; Pillared Framework; Luminescence; Crystal Structure;

The new thioindate–thioantimonate [Co(dien)2]2In2Sb4S11 (1, dien = diethylenetriamine) was prepared under solvothermal conditions and structurally characterized. 1 consists of 1-D inorganic [In2Sb4S11 4−]n chains constructed by bow-like trimeric [Sb3S7] units and heterometallic pseudosemicube [In2SbS4] clusters, and [Co(dien)2]2+ cations as counterions. The intermolecular H-bond interactions between 1-D inorganic [In2Sb4S11 4−]n anion and [Co(dien)2]2+ cation result in a 3-D supramolecular network.One new thioindate-thioantimonate [Co(dien)2]2In2Sb4S11 (1, dien = diethylenetriamine) was prepared under solvothermal conditions. 1-D inorganic [In2Sb4S11 4-]n chain of 1 is constructed by by nontetrahedra InS5 and SbS3 units. The intermolecular H-bond interactions between 1-D inorganic [In2Sb4S11 4-]n anion and [Co(dien)2]2+ cation result in a 3-D supramolecular network. 1 presents the rare example of a thioindate-thioantimonate combined with complex cation.Display Omitted► Although the structures of reported thioindates are constructed by building units involving only both InS4 and other MS4 tetrahedra (M = group 13 (Ga), group 14 (Ge, Sn), and some transition metal elements), relatively little progress has been made on thioindates with other nontetrahedra. ► 1 presents the only example of a thioindate-thioantimonate built of the combination of nontetrahedra SbS3 and [InS5] units with complex cation.
Keywords: Solvothermal synthesis; Thioindates; Thioantimonates; Crystal structure;

Synthesis and characterization of a tri-nuclear Co(II) complex with a Bis(catecholate) ligand by Yusaku Suenaga; Yuki Nakaguchi; Yasuhiro Fujishima; Hisashi Konaka; Koji Okuda (440-443).
A tri-nuclear Co(II) complex of formula [Co3(phen)3(L1)2] [L1 = 2,2′,3,3′-tetrahydroxy-benzaldazine, phen = 1,10-phenanthroline] has been prepared. The complex was characterized by X-ray crystal analysis, ESI-MS and its UV–Vis spectrum. The room temperature value of χm T is 7.50 emu K mol− 1, which is larger than the expected value of 5.58 emu K mol− 1 (for three isolated high spin Co(II) ions). When the temperature is lowered the χm T product continuously decreases down to 5.0 K, which indicates the presence of antiferromagnetic coupling between the CoII ions.Tri-nuclear Co(II) complex ([Co3(phen)3(L1)2]) with bis(catecholate) ligand (L1 = 2,2',3,3'-tetrahydroxybenzaldazine, phen = 1,10-phenanthroline) has been prepared. Two L1 molecules connect between three cobalt(II) ions which forms octahedral geometry with high spin state. We report herein the spectral characterization, crystal structure and magnetic property of the complex.Display Omitted► Tri-nuclear Co(II) complex with bis(catecholate) (L1) has been prepared. ► Two L1 molecules connect between Co(II) ions with high spin state. ► We described the crystal structure and the magnetic property of the complex.
Keywords: Tri-nuclear Co(II) complex; Bis(catecholate) ligand; X-ray crystal structure; Magnetic property;

Solvothermal synthesis, structure and properties of a new 3-D anionic porous framework by Man-Sheng Chen; Ying-Qun Yang; Chun-Hua Zhang; Dai-Zhi Kuang; Yi-Fang Deng; Zhi-Min Chen (444-446).
A new three-dimensional porous Zinc(II) metal-organic framework [NH2Et2][Zn(BTC)]·H2O (1) was synthesized by the self-assembly of 1,3,5-benzenetricarboxy acid (H3BTC) and Zn(II) salt in diethylformamide (DEF), and characterized by single-crystal X-ray structure determination, thermogravimetric analysis and X-ray powder diffraction studies. The adsorption behavior shows that compound 1 has selective adsorption capacities of CO2 over N2 after the removal of the water molecules within the pores.A novel 3D Zn(II) coordination polymer, [NH2Et2][Zn(BTC)]·0.5H2O (1) [BTC = 1,3,5-benzenetricarboxylate], has been solvothermally synthesized and characterized. Complex 1 shows a rare rtl topology net with selective adsorption capacities of CO2 over N2.Display Omitted► Three-dimensional anionic coordination framework. ► Solvothermal synthesis effect on formation and structure of the anionic metal-organic framework. ► Selective sorption behavior of CO2 over N2.
Keywords: Zinc(II) complex; Metal-organic framework; Solvothermal reaction; Gas adsorption;