Inorganic Chemistry Communications (v.53, #C)

Contents List (iii-ix).

Stereo-regulated methyl methacrylate (MMA) polymerization catalyzed by asymmetric Salen-type Schiff-base Cu(II) complexes by Yan Chen; Yaoju Liu; Xingmei Zhang; Zhao Zhang; Lin Liu; Daidi Fan; Liqin Ding; Xingqiang Lü (1-3).
A series of mononuclear asymmetric Salen-type Schiff-base complexes [Cu(Ln)] (n = 1–5, 15) were obtained by the Cu(II)-templated approach in the presence of one of five salicylaldehyde derivatives, respectively. These complexes could effectively catalyze the metal-coordinative polymerization of MMA for the formation of the syndio-enriched PMMAs (poly(methyl methacrylates)) in the presence of AIBN, where the Cu(II)-to-chelate-plane distances are positively relative to the catalytic activity. Moreover, the introduction of the encumbering substituent ortho to the phenoxide ring of the ligands plays a much more important and influential role on the tacticity and chain-growth of the obtained PMMAs than the variation of reaction conditions under the controllable polymerization.A series of asymmetric Salen-type Schiff-base complexes [Cu(Ln)] (1-5, n = 1-5) are shown to effectively catalyze the controllable polymerization of MMA, where Cu(II)-to-chelate-ring distance is postive to catalytic activity, while tacticity and chain-growth of the obtained syndio-enriched PMMAs rest with the introduction of an encumbering substituent ortho to the phenoxide ring of the ligands.Display Omitted
Keywords: Asymmetric Salen-type Schiff base Cu(II) complexes; Syndio-enriched atactic PMMA; Electronic and steric effect of substituents to the phenoxide rings;

A binodal tfz-d network constructed from trinuclear Cobalt(II) clusters by Xu-Dong Zhang; Ya-Meng Li; Lin Fan; Jian-Dong Pang; Zhan-Feng Ju (4-6).
A 3D network based on the trinuclear cobalt(II) clusters, [Co3(bta)2(bib)2] (1) (H3bta = 1,3,5-benzenetriacetic acid; bib = 1,3-bis(1-imidazoly)benzene), is synthesized and characterized. Topological analysis indicates that it has a unique binodal (3,8)-connected tfz-d network with the Schläfli symbol of (43)2(46·618·84). Interestingly, the magnetic data reveals the dominant antiferromagnetic interactions between the Co (II) cations within the trinuclear cluster.A 3D network based on the trinuclear cobalt(II) clusters, [Co3(bta)2(bib)2] (1) (H3bta = 1,3,5-benzenetriacetic acid; bib = 1,3-bis(1-imidazoly)benzene) have been synthesized and characterized. Topological analysis indicates that it has a unique binodal (3, 8)-connected tfz-d network with the Schläfli symbol of (43)2(46·618·84). The magnetic data reveals the dominant antiferromagnetic interactions between the Co (II) cations within the trinuclear cluster.Display Omitted
Keywords: Coordination polymers; Trinuclear cobalt (II); tfz-d network; Topology; Magnetic property;

Dinuclear cadmium(II) thiolate complexes bearing urea groups: Synthesis, characterization, photophysical properties and anion binding studies by Jing-Xiang Su; Yan-Yu Shen; Feng Ren; Zheng-Fang Lv; Xue-Chan Li; Zhou-Jia Lin; Hsiu-Yi Chao (7-10).
A series of cadmium(II) thiolate complexes with urea units [(bpy)2Cd(μ-SC6H4-4-NHC(O)NHC6H4-R-4)]2(ClO4)2 (R = NO2 (1), Cl (2), H (3); bpy = 2,2′-bipyridine), have been synthesized and characterized. The crystal structure of 3·(DMF)2 has been determined by X-ray diffraction. The photophysical properties and anion binding properties of 13 have been studied.Three dinuclear cadmium(II) thiolate complexes with urea units [(bpy)2Cd(μ-SC6H4-4-NHC(O)NHC6H4-R-4)]2(ClO4)2 (R = NO2 (1), Cl (2), H (3); bpy = 2,2′-bipyridine), have been synthesized. The selective color change of 1 towards F in DMSO provides an access for naked eye detection of F.Display Omitted
Keywords: Anions; Cadmium; Dinuclear; Thiolate; Urea;

A 3D metal–organic framework (MOF), {[Cd2(CTA)(bpp)2(H2O)2] (H2O)3}n (1) (H4CTA = cyclohexane-1,2,4,5-tetracarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane), has been synthesized and structurally characterized by elemental analysis, IR and powder X-ray diffraction. Single-crystal X-ray measurement reveals that the complex presents three-dimensional frameworks with 1D channels which are filled by unique (H2O)6 clusters. Noteworthily, the H4CTA ligands keep exclusive conformation, where the carboxyl groups adopt different coordination modes, and the bpp ligands perform two different conformations. Thermogravimetric analysis demonstrates that 1 features favorable thermal stability. Photoluminescence property of 1 is investigated in the solid state at room temperature as well.A 3D Cd(II) mixed-ligand MOF containing cyclohexane-1,2,4,5-tetracarboxylic acid and 1,3-bis(4-pyridyl)propane has been synthesized and structurally characterized. Six-molecule water clusters fill the 1D channels of the structural framework.Display Omitted
Keywords: Metal–organic framework; Cyclohexane-1,2,4,5-tetracarboxylic acid; Water cluster; Thermogravimetric analysis; Photoluminescence property;

The influences of the number of the ammonium groups and their arrangement manner on the photophysical properties of the quaternized zinc phthalocyanines were studied. The aggregation tendency, singlet oxygen generation ability and the fluorescence intensity properties of the quaternized zinc phthalocyanines were studied and compared. Results indicated that more quaternized ammonium groups and the straight chain arrangement manner for the quaternized zinc phthalocyanines can decrease aggregation degree and increase singlet oxygen generation and fluorescence intensity.Four quaternized zinc phthalocyanines with different ammonium groups and configuration for quaternized nitrogens were synthesized and studied. Result showed that the straight configuration and the increased numbers of quaternized ammonium groups can decrease the aggregation degree and improve the single oxygen generation ability and fluorescence intensity.Display Omitted
Keywords: Photodynamic therapy; Phthalocyanine; Quaternized nitrogen number; Molecular configuration; Singlet oxygen generation; Fluorescence intensity;

Hydrothermal reaction of the cyano-substituted derivative, NaN3, ZnCl2 and H4PMA (H4PMA = 1,2,4,5-benzenetetracarboxylic acid) yielded a dual-emissive coordination polymer: {[Zn2(PMA)(tzmb)2]∙6H2O}n (1) (tzmb =  N-(tetrazolmethyl)-4,4′-bipyridinium). In 1, the μ 2-κN2,κN6 tzmb and μ 4-bridging PMA4 − connect four-coordinated Zn(II) atoms to form a 2D (4,4)-connected topologic structure. The solid-state sample of 1 exhibits tunable blue-to-white-to-yellow photoluminescence (PL) upon variation of excitation wavelengths, and the PL appearance has been studied by the theoretical calculation.A dual-emissive zinc(II) coordination polymer, based on a new in-situ synthesized tetrazole derivative and benzenetetracarboxylic acid, was hydrothermally prepared and structurally characterized. The obtained polymer exhibits tunable blue-to-white-to-yellow fluorescence upon variation of excitation wavelengths and might be a good candidate for tunable luminescent material.Display Omitted
Keywords: Tetrazole; In-situ ligand synthesis; Photoluminescence; Hydrothermal reaction;

Novel drug delivery system for photoinduced nitric oxide (NO) delivery by Sushil Kumar; Rajan Kumar; Anand Ratnam; Narayan C. Mishra; Kaushik Ghosh (23-25).
A hybrid material (AB-1) was obtained by immobilizing photolabile ruthenium nitrosyl complex [Ru(LSBH)(PPh3)2(NO)Cl](ClO4) (1) into alginate polymer. A controlled release of nitric oxide was observed when a suspension of AB-1 was exposed to visible light. The amount of photoreleased NO from polymeric hybrid material was estimated using Griess reagent assay.Photoreleased nitric oxide (NO) from alginate hybrid material incorporating nitrosyl complex was transferred to reduced Mb and estimated the amount of NO using Griess reagent assay.Display Omitted
Keywords: Ruthenium nitrosyl complex; Polymer; Sol–gel preparation; Hybrid material incorporating nitrosyl complex; Griess reaction; NO delivery;

Compared to the difficult volatilization for germanium (IV) precursors, germanium (II) precursors usually have better volatilization but difficult to synthesize. A series of diamine germanium (II) precursors were synthesized, characterized and investigated by DFT calculations. These germanium (II) precursors were tested by TG experiments and showed excellent volatilization, which were suitable as a potential membrane material. Moreover, the Ge film was deposited on Si wafer directly and characterized by SEM.The diamine germanium (II) precursors were synthesized, characterized and investigated by DFT calculations. These germanium (II) precursors were tested by TG experiments and showed excellent volatilization, which were suitable as a potential membrane material. Moreover, the Ge film was deposited on Si wafer directly and characterized by SEM.Display Omitted
Keywords: Ge (II) precursors; Secondary amine ligands; Ge film; Thermal property; DFT calculations;

Binuclear O-bridged titanium(IV) complexes of phenylenediamine-bis(phenolato) ligands were obtained from the corresponding ligands and Ti(OiPr)4 and analyzed by 1H, 13C and diffusion NMR. The comparative hydrolytic stability in 1:9 D2O/DMSO-d 6 was assessed by 1H NMR, and the complexes featured t 1/2 values of above 100 h. The cytotoxic activity of the binuclear complexes was measured toward human colon HT-29 cancer cell line by the MTT assay. Although as expected most complexes exhibited mild or no cytotoxic activity, one leading complex demonstrated marked activity with IC50 value of 77 ± 40 μM.Binuclear, inert Ti(IV) complexes were synthesized in high yields. One leading complex shows marked cytotoxic activity toward colon HT-29 cells, where ligand substitution affects the complex reactivity.Display Omitted
Keywords: Titanium(IV); Phenolato ligands; Cytotoxicity; Metallodrugs; Cisplatin;

Two novel Ag(I) complexes zero-dimensional (0D) [Ag(ibz)(Hibz)]2 (Ag1) (Hibz = 4-(1H-imidazolyl)benzoic acid) and two-dimensional (2D) [Ag(imbz)(Himbz)]n (Ag2) (Himbz = 4-(1H-imidazolyl-1-methyl)benzoic acid) have been synthesized through the hydrothermal method. By changing the ligands from rigid Hibz to flexible Himbz, the distance between two aromatic rings in the ligand is controlled to get different dimensional complexes. Both complexes have been characterized by single-crystal X-ray diffraction, infrared (IR), elemental analysis and thermal gravimetric analyses (TGA). Ag1 is coordinated with two nitrogen atoms, forming a two-coordination linear configuration. While Ag2 possesses interesting 2D frameworks, exhibiting two-fold interpenetrating sql topology structure. The luminescent properties of Ag1 and Ag2 are investigated both in the solid state and in different solvents (DMSO, CH3CN and CH3OH) at 298 K and 77 K. Ag1 displays stable blue luminescent in the solid state and in solvents at 298 K and 77 K. Whereas, Ag2 shows tunable luminescence by changing the temperature from 298 K to 77 K, indicating thermochromic luminescence for Ag2. The emission efficiency of Ag1 and Ag2 is found with quantum yields ranging from 0.073 to 0.208, which is much higher than that of free ligand.Two novel Ag(I) complexes [Ag(ibz)(Hibz)]2 (Ag1) and [Ag(imbz)(Himbz)]n (Ag2) have been synthesized. Ag1 shows 0D two-coordination linear configuration, "while" Ag2 possesses 2D framework, exhibiting two-fold interpenetrating sql topology structure. Ag1 displays stable blue luminescence and Ag2 shows tunable luminescence by changing the temperature from 298 K to 77 K.Display Omitted
Keywords: Ag(I) complexes; Flexible imidazole ligands; Photoluminescent properties; Quantum yield;

Solvothermal reaction of Ba(NO3)2 with 5-(4-(2,6-di(pyridin-4-yl)pyridin-4-yl)phenoxy) isophthalic acid (H2L) afforded the first metal–organic framework based on L2 − ligand, [Ba2L2(H2O)3] n ·5.5nH2O (1). Single crystal X-ray analysis shows that MOF 1 features a novel 3D supramolecular network built by different monochiral sheets. The luminescence intensity of this MOF can be modulated by different organic solvents.One new Ba-MOF was synthesized based on H2L ligand for sensing of small molecules. The MOF consisted of left- and right-handed-helical chiral sheets, and the adjacent sheets are further linked by inter-sheet hydrogen bonds to generate a 3D supramolecular achiral network.Display Omitted
Keywords: Metal–organic framework; 5-(4-(2,6-Di(pyridin-4-yl)pyridin-4-yl)phenoxy)isophthalic acid; Helical chains; Chiral sheets; Luminescence;

The first use of H4nbtc ligand afford a novel 2D Cu(II) metal-cluster-based coordination polymer (MCCP), [Cu4(nbtc)1.5(μ 3-OH)2(H2O)4·8H2O (1) (H4nbtc = 6,6′-dinitro-2,2′,4,4′-biphenyl tetracarboxylic acid), in which the boat- and chair-shaped tetranuclear cooper (II) clusters [Cu4(μ 3-OH)2]6+ coexist unprecedentedly. Interestingly, the chair-shaped CuII 4 cluster-based 1D ladder chain perfectly threaded into the rectangle windows of the 2D grids constructed by boat-shaped CuII 4 clusters and H4nbtc. And the magnetic property has also been investigated.The first use of H4nbtc ligand afforded a novel 2D Cu(II) MCCPs, in which the boat-shaped and chair-shaped CuII 4 clusters [Cu4(μ 3-OH)2]6 + coexist unprecedentedly. Interestingly, the chair-shaped CuII 4 cluster-based 1D ladder chain threaded into the rectangle windows in the 2D grids formed by boat-shaped CuII 4 clusters and nbtc ligands.Display Omitted
Keywords: Coordination polymers; Boat; Chair; Tetranuclear cooper (II) cluster;

A novel non-interpenetrated lanthanide–organic framework constructed by dinuclear cerium cluster as pillar and trinuclear cerium cluster as layer with a uniform (3,8)-connected topology has been reported, which exhibits mesoporous cages between layers and 3D interconnected channels.A novel mesoporous non-interpenetrated lanthanide–organic framework constructed by dinuclear cerium cluster as pillar and trinuclear cerium cluster as layer with a uniform (3,8)-connected topology has been reported.Display Omitted
Keywords: Lanthanide–organic framework; Mesoporous materials; Topological structure; Secondary building units;

Toward chiral iron(II) spin-crossover grafted resins with imidazole Schiff-base ligands by Lei Tian; Chun-Yan Pang; Feng-Li Zhang; Long-Fang Qin; Zhi-Guo Gu; Zaijun Li (55-59).
Using chiral imidazole Schiff-base as ligands, two couples of mononuclear iron(II) enantiomeric complexes fac-Λ-[Fe(R-L)3](ClO4)2·H2O (1), fac-Δ-[Fe(S-L)3](ClO4)2·H2O (2), fac-Λ-[Fe(R-L)3](BF4)2·H2O (3), fac-Δ-[Fe(S-L)3](BF4)2·H2O (4) (L = 1-(2-naphthyl)-N-((1-methyl-imidazol-2-yl)methylene)ethanamine) have been successfully synthesized and characterized. The CD spectra of 1 and 2, 3 and 4, were basically mirror images confirming their enantiomers. X-ray crystallography revealed that complexes 14 all crystallized in the chiral space group P213 with the iron(II) center surrounded by three bidentate ligands. Magnetic measurements revealed incomplete spin transition for 1, and gradual spin crossover (T 1/2  = 150 K) for 3. However, the spin-crossover behaviors were vanished after grafting 14 to the Merrifield's peptide resin, and the iron(II) centers in the resin remained in a high-spin state in the temperature range of 2–300 K.Two couples of mononuclear spin-crossover iron(II) enantiomeric complexes 14 and their Merrifield's peptide resin-supported chiral compounds 58 have been successfully synthesized. Magnetic measurements revealed that monomer complexes 14 displayed obvious spin-crossover properties, while the spin-crossover behavior presented in monomer complexes 14 was vanished after it was grafted to the resin.Display Omitted
Keywords: Chiral; Iron(II); Spin-crossover; Enantiomers; Polymer;

Novel organic–inorganic hybrid monomeric Keggin-type phosphotungstate containing heterometallic {Ni6WNi} clusters by Jing-Wen Liu; Yong-Chao Liu; Huan He; Bai-Feng Yang; Guo-Yu Yang (60-63).
A novel octanuclear heterometallic {Ni6WNi}-substituted Keggin-type phosphotungstate [Ni(H2O)(en)2][WO4]{[Ni6(OH)3(H2O)2(en)3(Im)2](B-α-PW9O34)}·2H2O (1) with mixed organic ligands of en and Im (en = ethylenediamine, Im = Imidazole) has been hydrothermally synthesized and structurally characterized by IR spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Notably, 1 is an interesting spoon-shaped monomeric polyoxometalate consisting of mixed organic ligands and unprecedented octanuclear heterometallic {Ni6WNi} cores where the WO4 tetrahedron is linked to the triangular {[Ni6(OH)3(H2O)2(en)3(Im)2](B-α-PW9O34)} clusters and [Ni(H2O)(en)2]2 + cations through Ni–Ot–W linkages. Magnetic susceptibility measurements indicate ferromagnetic coupling within 1.A unique novel octanuclear heterometallic {Ni6WNi}-substituted Keggin-type phosphotungstate [Ni(H2O)(en)2][WO4]{[Ni6(OH)3(H2O)2(en)3(Im)2](B-α-PW9O34)} · 5H2O (1, en = ethylenediamine, Im = Imidazole) has been hydrothermally made. It is an interesting spoon-shaped monomeric polyoxometalate containing {Ni6WNi} cores linked by the WO4 group, observed firstly in polyoxometalate chemistry.Display Omitted
Keywords: Polyoxometalates; Hydrothermal synthesis; Heterometallic; Organic–inorganic hybrid; Nickel;

A novel polyoxometalate (POM)-based metal-organic compound constructed from a multinuclear AgI cluster and Keggin-type [VW12O40]3 − anion, [Ag4(Hpyttz)2(H2pyttz)][HVW12O40]·3H2O (1) (H2pyttz = 5′-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole), was hydrothermally synthesized and characterized by IR spectroscopy, TG analysis, powder and single-crystal X-ray diffraction. In compound 1, [VW12O40]3 − (VW12) was in-situ transformed from [SiW12O40]4 − anion. Eight AgI ions were connected by six Hpyttz/H2pyttz ligands with three coordination modes forming an unprecedented [Ag8(Hpyttz)4(H2pyttz)2] cluster, which connected with six VW12 anions to construct a 2-D double-layer (3,6)-connected network with {43}2{46.66.83} topology. Moreover, the photocatalytic activity of 1 has been investigated.A novel [VW12O40]3 −-based 2D (3,6)-connected metal-organic compound containing an unprecedented [Ag8(Hpyttz)4(H2pyttz)2] cluster has been obtained, in which the [VW12O40]3 − anion was in-situ transformed from the [SiW12O40]4 − anion. The octa-nuclear AgI cluster represents the highest multi-nuclear AgI subunit in [VW12O40]3 −-based MOCs. The title compound shows photocatalytic activity toward the decomposition of MB.Display Omitted
Keywords: Polyoxometalate; Bi(triazole) derivative; Multi-nuclear AgI cluster; Metal-organic compound; Photocatalytic property;

Synthesis and characterization of palladium (II) complex of Schiff base ligand: C―S bond cleavage and catalytic activity by Poulami Pattanayak; Debprasad Patra; Paula Brandão; Dasarath Mal; Vitor Felix (68-71).
Reaction of ligand, L-CH2Ph with Pd(CH3CN)2Cl2 in acetonitrile in presence of PPh3 and subsequent addition of NaClO4 yielded Pd(II) complex, [Pd(L)(PPh3)](ClO4) 1 due to the S―C (CH2Ph) bond cleavage during complexation. Complex 1 was characterized by spectral analysis and the structure was authenticated by single crystal X-ray diffraction. The diffraction analysis revealed that the monoanionic ligand binds with palladium (II) in (N, N, S) fashion in a distorted square planar geometry where the fourth position is occupied by one tri phenyl phosphine group. One ClO4 ion satisfies the charge of the former aggregate, [Pd(L)(PPh3)]+. The complex [Pd(L)(PPh3)](ClO4), 1 exhibits a very good catalytic activity towards C―C bond formation.Newly designed Schiff base ligand, L-CH2Ph and its palladium complex, [Pd(L)(PPh3)](ClO4) have been synthesized and characterized unequivocally. The complex shows catalytic activity towards C―C bond formation in presence of air and moisture.Display Omitted
Keywords: Palladium (II); C―S bond cleavage; Square planar; Suzuki and Heck reactions;

Synthesis, crystal structure and electrocatalytic activity of discrete and polymeric copper(II) complexes with bitopic bis(pyrazol-1-yl)methane ligands by Andrei S. Potapov; Eugenia A. Nudnova; Andrei I. Khlebnikov; Vladimir D. Ogorodnikov; Tatiana V. Petrenko (72-75).
New coordination copper(II) compounds containing bitopic bis(pyrazol-1-yl)methane ligands, namely 1,1,2,2-tetrakis(pyrazol-1-yl)ethane, 1,4-bis[bis(pyrazol-1-yl)methyl]benzene and 1,4-bis[bis(3,5-dimethylpyrazol-1-yl)methyl]benzene were prepared. Reactions of ligands with Cu2 + ions in 1:2 ratio gave discrete homodinuclear complexes, while 1:1 ligand-to-metal ratio lead to the formation of coordination polymers. Electrocatalytic activity of compounds in oxygen electroreduction reaction on the surface of modified carbon paste electrode was evaluated.New coordination copper(II) compounds containing bitopic bis(pyrazol-1-yl)methane ligands, namely 1,1,2,2-tetrakis(pyrazol-1-yl)ethane, 1,4-bis[bis(pyrazol-1-yl)methyl]benzene and 1,4-bis[bis(3,5-dimethylpyrazol-1-yl)methyl]benzene were prepared.Display Omitted
Keywords: Bis(pyrazol-1-yl)methane; Copper(II); Bitopic ligands; Coordination polymers; Crystal structure; Electrocatalytic activity;

Robust metal–organic framework with [Mn3] clusters: Synthesis, structure and magnetic property by Zhan-Yun Zhang; Peng-Fei Shi; Huan-Cheng Hu; Zhi-Lei Wu; Jian-Zhong Cui; Bin Zhao (76-79).
In this work, one novel three dimensional non-interpenetrated metal–organic framework {[Mn3(L)2(H2O)4]·2H2O·2DMF}n (1) was synthesized by a new tri-carboxylic ligand (H3L = 3,5-Bis-[2-(4-carboxy-phenoxy)-ethoxy]-benzoic acid). Single crystal structural determination revealed that compound 1 possesses a stable 3D framework, containing linear tri-nuclear [Mn3] cluster as a node. The investigation on PXRD patterns in various solvents and TGA displays excellent solvents and thermal stability. Additionally, magnetic measurements indicate that antiferromagnetic interactions exist within compound 1.One novel three dimensional non-interpenetrated metal–organic framework was synthesized by a new tri-carboxylic ligand and Mn(II) ions. The compound is characteristic of linear Mn3 cluster as a node, and displays excellent solvents and thermal stability. Magnetic measurements indicate that antiferromagnetic interactions exist within this compound.Display Omitted
Keywords: Metal–organic framework; Tri-nuclear cluster; Solvents and thermal stability; Magnetic property;

Tuning peripheral π-stacking motifs in {Cr(tpy)2}3 + domains (tpy = 2,2′:6′,2″-terpyridine) by Jonas Schönle; Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger (80-83).
The homoleptic complexes [Cr(1)2][PF6]3 and [Co(1)2][PF6]3 (1  = 4′-(naphth-2-yl)-2,2′:6′,2″-terpyridine) have been prepared and structurally characterized. The packing interactions in both complexes are identical, consisting of a combination of naphthyl…naphthyl π-stacking interactions and double naphthyl…pyridine embraces generating chains of cations with alternating long and short M…M contacts.In the solid state, the isostructural complexes [Cr(1)2][PF6]3 and [Co(1)2][PF6]3 (1  = 4′-(naphth-2-yl)-2,2′:6′,2″-terpyridine) exhibit packing interactions which combine naphthyl…naphthyl π-stacking interactions and double naphthyl…pyridine embraces generating chains of cations with alternating long and short M…M contacts.Display Omitted
Keywords: Chromium; Cobalt; Terpyridine; Naphthyl; Crystal structure; π-Embraces;

Pillar-layered Zn–triazolate–carboxylate frameworks tuned by the bend angles of ditopic ligands by Ni Bai; Shu'ni Li; Yucheng Jiang; Mancheng Hu; Quanguo Zhai (84-87).
In the utilization of three ditopic ligands with different bend angles as pillars, we reported herein three pillar-layered Zn–triazolate–carboxylate frameworks, namely, [Zn2(ATRZ)2(BDC)] n (1), [Zn2(ATRZ)2(TPDC)] n ·2nDMF (2) and [Zn2(ATRZ)2(ADDC)] n (3) (ATRZ = 3-amino-1,2,4-triazole, H2BDC = 1,4-benzenedicarboxylic acid, H2TPDC = 2,5-thiophenedicarboxylic acid, and H2ADDC = 1,3-adamantanedicarboxylic acid). Single crystal structural analyses demonstrate that different geometries of ditopic carboxylate pillars not only result in Zn–ATRZ layers adopting various corrugated configurations, but also give rise to 3,4-connected self-interpenetrated net of 1 and non-interpenetrated nets of 2 and 3. All these compounds exhibit high thermal stability and blue photoluminescence.Reported herein three 3D pillar-layered MOFs designed by appropriate selection of well-known Zn–triazolate motifs as 2D layers, and ditopic aromatic carboxylate ligands as pillars.Display Omitted
Keywords: 1,2,4-Triazole; Ditopic carboxylic acid; Metal–organic frameworks; Pillared-layer structure;

A series of new emissive mononuclear copper(I) bipyridyl complexes bearing the methoxycarbonyl groups by Jing-Lin Chen; Xing-Feng Fu; Jin-Yun Wang; Zong-Hao Guo; Yi-Liang Xiao; Li-Hua He; He-Rui Wen (88-91).
A new series of mononuclear copper(I) complexes 13 possessing functionalized 6-methoxycarbonyl-2,2′-bipyridine and phosphine mixed ligands have been synthesized and characterized. Each Cu(I) atom gives an N2P2 distorted tetrahedral configuration, in which the dihedral angles between two pyridyl rings follow a ranking of 1 (4.640°) <  2 (av. 9.065°) <  3 (15.648°), while a reverse order lies in the dihedral angles between the methoxycarbonyl and its conjoined pyridyl ring (1 (15.224°) >  2 (av. 8.983°) >  3 (2.786°)). Complexes 13 show a weak low-energy absorption band at 330–500 nm in CH2Cl2 solution, ascribed to charge-transfer transitions with appreciable 1MLCT character, as supported by TD-DFT calculations. The solid-state luminescence is observed in 13 at room temperature, which is affected by the phosphine, the substituents on the 2,2′-bipyridyl, and the above-mentioned dihedral angles.A new series of mononuclear Cu(I) complexes 13 with functionalized 6-methoxycarbonyl-2,2′-bipyridine and phosphine mixed ligands have been synthesized and characterized. The solid-state luminescence properties of 13 are influenced by the phosphine ancillary ligand and the substituents of the 2,2′-bipyridyl ring.Display Omitted
Keywords: Copper(I); Crystal structure; Photoluminescence; 6-Methoxycarbonyl-2,2′-bipyridine;

Magnetic cobalt nanoparticles, stabilized using ionic liquid [bmim]BF4, have been used for catalyzing aza- and thia-Michael reactions under environmentally benign conditions at room temperature. The products were isolated in high yields in short reaction times, while the catalyst was efficiently recycled multiple times using a magnetic field.Display Omitted