Inorganic Chemistry Communications (v.54, #C)

Contents List (iii-x).

A new synthetic route to the trispyrrole iron(II) complex {K(dme)4[tpaMesFe]} was established starting from BOC-protected pyrrol via synthesis of the corresponding boronic acid, cross-coupling reaction, deprotection, triple Mannich reaction, a deprotonation and finally a salt metathesis. The complex was characterized and applied in iron-catalyzed coupling reactions. In more detail, with catalytic amounts of K(dme)4[tpaMesFe] the homo-coupling of aromatic Grignard reagents as well as the hetero-coupling of aromatic Grignard reagents were feasible. Noteworthy, to force the reaction nitrous oxide was added to realize yields up to 93% at mild reaction conditions.Display Omitted
Keywords: Iron; Tetradentate ligand; Amine ligand; Amide ligand; Coupling reaction;

Single molecule magnet of 2D Salen-type dysprosium coordination polymer by Yumei Yue; Pengfei Yan; Jingwen Sun; Guangming Li (5-8).
A new flexible Salen-type dysprosium coordination polymer, [Dy2(H2L)2(NO3)4(CH3O)2]n (1) (H2L = N,N′-bis(salicylidene)-1,4-butane-diamine), has been synthesized by a solvothermal method. The single-crystal X-ray diffraction studies reveal that complex 1 features a two dimension (2D) network structure with rare dinuclear units. Each Dy(III) ion is eight-coordinated where the μ2-(OCH3)2 bridged Dy2O2 cores are linked by four Salen-type ligands in bidentate fashion. Magnetic studies reveal that complex 1 presents antiferromagnetic interactions between Dy(III) centers and exhibits the frequency dependent peaks, a behavior characteristic of a single-molecule magnet.The flexible Salen-type dysprosium complex represents 4f SMMs with the 2D coordination networks from rare methoxy-O bridged dinuclear units.Display Omitted
Keywords: Salen-type; Dysprosium coordination polymer; Single molecular magnet; Flexible; Dinuclear;

Hydrothermal synthesis has afforded a 3D copper(II) metal–organic framework (MOF) based on a new rigid bis(triazole)-based ligand, namely, {[Cu3(btb)3(nbta)2]·(H2O)2} n (btb = 4,4′-bis(1,2,4-triazolyl-1-yl)-biphenyl, H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid), which has been characterized by IR, elemental analysis, thermal gravimetric and single-crystal X-ray diffraction. The structural analyses reveal that title complex displays a rarely 3D trinodal (3,4,4)-connected network with 3,4,4T20 topology. Further, fluorescence and excellent adsorption properties for congo red dye of the compound have been investigated.A 3D framework has been constructed by the assembly of CuII center with rigid bis(triazole)-based ligand and 5-nitro-1,2,3-benzenetricarboxylic acid, which features a unique 3,4,4T20 topology. The results of adsorption experiment show that the complex presents high efficiency for adsorbing congo red.Display Omitted
Keywords: Adsorption; Bis(triazole); Coordination polymer; Copper(II); Fluorescence property;

A new luminescent complex constructed by oxomolybdate and 3,5-di(4H-1,2,4-triazol-4-yl)benzoic acid via Mo–N bonds by Bin Liu; Ying-Hui Yu; Wen-Hong Jiang; Guang-Feng Hou; Jin-Sheng Gao (12-15).
A new complex namely, [(Mo2O6)L]·CH3OH·3H2O (1), based on oxomolybdate and 3,5-di(4H-1,2,4-triazol-4-yl)benzoic acid (L) was synthesized under hydrothermal condition, which shows a new three-dimensional supramolecular framework with unreported topological structure. In addition, the luminescent and electrochemical behaviors of complex 1 were investigated.A triazole-MoIV complex is hydrothermally synthesized with interesting 3D supramolecular framework with unreported topological structure and fluorescence and electrochemical properties.Display Omitted
Keywords: Coordination polymers; Triazole; Oxomolybdate; Luminescent; Electrochemical;

The complex cations [Pt0(C3Ph3)(PPh3)2]+ and [Pt0(C3Ph3)(tripod)]+ with tripod = CH3C(CH2PPh2)3 contain the smallest Hückel aromat C3R3 + (with n = 0) as ligand. Since this cation is a CT acceptor, the complexes are characterized by low-energy (Pt0 to C3Ph3 +) MLCT states. The complexes show a photoluminescence which originates from the lowest MLCT triplet.The complex cations [Pt(0)(C3Ph3)(PPh3)2]+ and [Pt(0)(C3Ph3)(tripod)]+ are characterized by a low-energy (Pt0 to C3Ph3 +) MLCT excited state. The luminescence of both cations originates from the lowest MLCT triplet.Display Omitted
Keywords: Luminescence; MLCT; Platinum(0); Cyclopropenium ligand; Phenylphosphine ligands;

A novel transition-metal-linked hexaniobate cluster with photocatalytic H2 evolution activity by Zhijie Liang; Dongdi Zhang; Qisen Liu; Pengtao Ma; Jingyang Niu; Jingping Wang (19-20).
A novel transition-metal (TM) complex based on Lindqvist polyoxoniobate K10[(Nb6O19)CrIII(H2O)2]2·28H2O (1) has been synthesized by a new two-pot synthesis strategy and structurally characterized by single crystal X-ray diffraction analysis, IR spectrum, UV–vis spectroscopy, XRPD and TG analysis. Compound 1 crystallizes in the C2/m space group with a  = 32.143(19) Å, b  = 10.030(6) Å, c  = 12.878(8) Å, β  = 110.611(9)°, and V  = 3886(4) Å3. X-ray structure analysis reveals that polyanion [(Nb6O19)CrIII(H2O)2]2 10 − (1a) represents the first example of two nuclear dimeric polyoxoniobate, in which two Lindqvist anions [Nb6O19]8 are sandwiched by two {CrIII(H2O)2} groups. Further, 1 exhibits photocatalytic H2 evolution activity.The first two-nuclear sandwich PONb, K10[(Nb6O19)CrIII(H2O)2]2·28H2O (1), has been synthesized, and the photocatalytic activity of 1 has also been studied.Display Omitted
Keywords: Polyoxoniobate; Transition metal; Photocatalytic; Crystal structure;

Crystal structures and biological activities of a symmetrical quinoline thioether ligand and its transition metal complexes by Xun-Zhong Zou; Jing-An Zhang; Li-Jie Zhang; Ya-Jie Liu; Ning Li; Yu Li; Shi-Chao Wei; Mei Pan (21-24).
The ligand 2,6-bis (8-quinolinylthiomethyl) pyridine and its four transition metal complexes have been synthesized and characterized by elemental analysis (EA), infrared spectra (IR) and single-crystal diffraction. It was revealed that compounds 13 were comprised of discrete mononuclear units and double nuclear structure in compound 4. The antibacterial activities and pesticide activities of the ligand and complexes 14 were tested. The results showed that some compounds had absolute specificity for certain bacteria, and could have good application prospect in pharmaceutical and agricultural use.Fig. 1(a) view of the coordination environment of Cu(II) ions in 1. (b) View of the coordination environment of Cd(II) ions in 2. (c) View of the coordination environment of Zn(II) ions in 3.Display Omitted
Keywords: 2,6-Bis (8-quinolinylthiomethyl) pyridine; Transition metal complexes; Antibacterial activities; Pesticide activities;

A novel organic–inorganic hybrid independent 1-D double-chain silicotungstate [Cu(biim)2][Cu(4,4′-bpy)(biim) (H2O)][α-SiW12O40]·3H2O (1, biim = 2,2′-biimidazole, 4,4′-bpy = 4,4′-dipyridine) has been successfully synthesized by reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, EuCl3, biim and 4,4′-bpy under 160 °C hydrothermal environment and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The most remarkable structural feature of 1 is that two types of independent 1-D chains are paralleling and one is constructed from plenary Keggin [α-SiW12O40]4 − units and [Cu(biim)2]2 + linkers while the other is based on [Cu(biim)(H2O)]2 + cations and 4,4′-bpy connectors. The variable-temperature magnetic susceptibility of 1 shows the weak antiferromagnetic exchange interactions within CuII centers. Furthermore, the solid-state electrochemical properties of 1 have been also measured in 0.5 mol·L− 1 Na2SO4  + H2SO4 aqueous solution by entrapping it in a carbon paste electrode.An organic−inorganic hybrid independent 1-D double-chain Keggin-type silicotungstate with mixed ligands has been synthesized and characterized.Display Omitted
Keywords: Silicotungstate; 1-D double chain; Hydrothermal environment; Electrochemistry; Magnetism;

A dinuclear tris(3,5-diisopropyl-pyrazolyl borate) (Tpy iPr2) based cadmium hydroxo complex, [(TpyiPr2)2Cd2(μ-OH)(μ-PziPr2)](DCM)5, has been synthesized and characterized by the single crystal X-ray diffraction technique. Structural analysis shows that the two Cd-TpyiPr2 moieties are bridged by one hydroxide and one pyrazolate molecule. Hydrolytic activity of the complex was checked using 4-nitro phenylacetate as the substrate. The pseudo-first order rate constant calculated on the basis of kinetic study was 1.535 × 10− 4  s− 1 while the second order rate constant was 0.226 M− 1  s− 1.A novel dinuclear cadmium hydroxo complex, [(TpiPr2)2Cd2(μ-OH)(μ-PziPr2)](DCM)5, has been synthesized and characterized by the single crystal X-ray diffraction technique. The two Cd-Tpy iPr2 moieties are bridged by one hydroxide and one pyrazolate molecule. Hydrolytic activity of the complex by 4-nitro phenylacetate shows that the complex is a nucleophile.Display Omitted
Keywords: Cadmium; Hydroxide; Ester hydrolysis; Kinetic study; Crystal structure;

Synthesis and characterization of decanuclear Ln(III) cluster of mixed calix[8]arene-phosphonate ligands (Ln = Pr, Nd) by Kongzhao Su; Feilong Jiang; Jinjie Qian; Jiandong Pang; Falu Hu; Salem M. Bawaked; Mohamed Mokhtar; Shaeel A. AL-Thabaiti; Maochun Hong (34-37).
Two novel decanuclear Ln(III) compounds (Ln = Pr for 1, Nd for 2) have been solvothermally obtained by using p-tert-butylcalix[8]arene (H8TBC8A) and phenylphosphonate (PhPO3H2) as ligands. Single crystal X-ray diffraction studies reveal that both compounds are stacked by dumbbell-like Ln10 clusters, which are capped by two TBC8A8 − supports and linked by four complementary PhPO3 2 − ligands as well as other bridging anions. In addition, the self-assembly behavior of both compounds is interesting: the cationic Ln10 cluster layers are separated by the layers of H6TBC8A2 − ligands. Moreover, the luminescent and magnetic properties of both compounds were examined.Utilizing phosphonate as co-ligand, two novel decanuclear Ln10 clusters (Ln = Pr, Nd) based on p-tert-butylcalix[8]arene (H8TBC8A) with interesting self-assembly properties are reported: the cationic Ln10 cluster layers are separated by the anionic layers of co-crystallized H6TBC8A2 − ligands.Display Omitted
Keywords: Calixarenes; Cluster compounds; Photoluminescent properties; Magnetic properties; Lanthanides;

Selective reduction of a wide range of aromatic and aliphatic aldehydes to the corresponding alcohols with NaBH4 was achieved in the presence of an oxovanadium(IV) Schiff base complex encapsulated in the nanopores of zeolite Y (VOL-Y). For most of the aldehydes, a conversion of 100% was observed after less than 5 min. High chemoselectivity of the reduction for aldehydes over ketones was verified by a competitive reduction between 4-methylbenzaldehyde and acetophenone.Selective reduction of a wide range of aromatic and aliphatic aldehydes to the corresponding alcohols with NaBH4 was achieved in the presence of an oxovanadium(IV) Schiff base complex encapsulated in the nanopores of zeolite-Y (VOL-Y).Display Omitted
Keywords: Reduction; Aldehyde; Ketone; Heterogeneous catalyst; Zeolite-Y; Schiff base;

By incorporating triamine-triazines as hydrogen bonding sites into the fragment of the ligand, cerium-based metal–organic tetrahedron Ce-TBMN has been used as an artificial chemosensor for selective recognition of guanosine over other ribonucleosides. With the size constraint of the tetrahedron, Ce-TBMN showed the selective fluorescent response of GMP among the twelve ribonucleotides.By incorporating triamine-triazin as hydrogen bonding sites into the fragments of the ligands, Cerium-based metal–organic tetrahedron Ce-TBMN containing naphthalene fluorophore units has been used as an artificial chemosensor for selective recognition of guanosine over other ribonucleosides. Moreover, the size constraint of the tetrahedron benefited the selective fluorescent detection of GMP among the twelve ribonucleotides.Display Omitted
Keywords: Metal–organic tetrahedron; Hydrogen bonding; Size constraint; Selective recognition; Nucleotides;

Synthesis, crystal structures and sensitivity to sunlight of two Ag (I) photoresponsive metal–organic complexes by Hai-Juan Du; Wen-Li Zhang; Chao-Hai Wang; Yao Li; Yun-Yin Niu; Hong-Wei Hou (45-49).
Two Ag (I) photoresponsive metal–organic complexes have been constructed from viologen derivatives 1, 1″-[1, n-phenylene-bis(methylene)]bis-4, 4′-bipyridinium-bisbromide (n = 2 and 3) cationic ligands and silver bromide upon slow self-assembly at room temperature. They are characterized by single crystal X-ray diffraction, powder X-ray diffraction, thermal gravimetric analysis (TGA), UV–vis, IR and ESR spectra. Compound 1 is a 3D folding framework and compound 2 contains a 1D inorganic chain constructed by (AgBr3)2 − polyhedral units. In addition, the photochromic behaviors of compounds 1 and 2 were also investigated, and they show different and obvious fast photoresponse rate under sunlight.Two Ag (I) photoresponsive metal–organic complexes with different and obvious fast photoresponse rate under sunlight have been constructed from viologen derivatives 1, 1″-[1, n-phenylene-bis(methylene)]bis-4, 4′-bipyridinium-bisbromide (n = 2 and 3) cationic ligands and silver bromide upon slow self-assembly at the room temperature.Display Omitted
Keywords: Improved sensitivity; Photoresponsive metal–organic complexes; Sunlight; Photoresponse rate;

Two new sandwich mixed (phthalocyaninato)(porphyrinato) europium triple-decker (TDMAPP)Eu2[Pc(OPh)8]2 (1) and (TPyP)Eu2[Pc(OPh)8]2 (2) were designed and synthesized. The self-assembled aggregates of 1 and 2 were fabricated by means of a solution-based quasi-Langmuir–Shäfer (QLS) method. Both structures and properties of the aggregates of 12 were comparatively studied by UV–vis absorption spectroscopy, atomic force microscopy (AFM), X-ray diffraction (XRD) techniques and current–voltage (I–V) measurements. Experimental results indicated that the molecules of 1 in the self-assembled aggregates adopted a typical J-type (edge-to-edge) aggregation mode, whereas those of 2 took a “face-to-face” conformation and “edge-on” orientation, implying the effect of side-group substituents on tuning the intermolecular stacking. XRD and AFM characterization clearly showed evidence for the formation of highly textured film structures with controlled molecular orientations within the self-assembled aggregates of 1, while a dimeric supramolecular structure was revealed and thus as the building block self-assembles into the target the net-like nanostructures for the aggregates of 2. In addition, the highly ordered film of 1 showed good semiconducting property with a conductivity of ca. 2.35 × 10− 5  S·cm− 1, which is more than ca. 1 order of magnitude higher than those of 2, closely related to micro-structures and morphology found for the self-assembled aggregates.Two novel sandwich triple-deckers were synthesized, and fabricated into self-assembled aggregates by using a solution-based method. Comparative investigation results reveal that the substituent groups play a critical role on tuning the intermolecular stacking, and in turn impact on electrical conductivity of materials.Display Omitted
Keywords: Phthalocyanine; Porphyrin; Rare earth triple-decker complex; Aggregation; QLS method;

Spillover enhanced hydrogen storage in Pt-doped MOF/graphene oxide composite produced via an impregnation method by Hu Zhou; Jun Zhang; Jian Zhang; Xiu-Fen Yan; Xiao-Ping Shen; Ai-Hua Yuan (54-56).
Pt-doped MOF/graphene oxide (GO) composites were synthesized via a colloidal Pt nanoparticle (NP) incipient-wetness impregnation method for the first time. The composites Pt@HKUST-1/GO and Pt@ZIF-8/GO were characterized by X-ray diffraction, electron microscopy and gas adsorption. The hydrogen uptakes of both composites at 298 K and 860 mm Hg were enhanced by a factor of 3.6 or 4.1 compared to MOFs, although Pt NPs were obviously aggregated throughout MOF/GO networks. This significant enhancement is mainly attributed to the combination of high porosities of MOF/GO supports and hydrogen spillover mechanism, in which Pt NPs and MOF/GO act as dissociation source and receptor, respectively.Pt-doped MOF/graphene oxide (GO) composites were prepared via an incipient-wetness impregnation method for the first time. The significantly enhanced hydrogen uptakes at 298 K for composites compared to pristine-MOFs can be attributed to the spillover mechanism, where Pt nanoparticles and MOF/GO act as dissociation source and receptor, respectively.Display Omitted
Keywords: Hydrogen storage; MOFs; Graphene oxide; Platinum; Impregnation;

A novel entangled coordination polymer presenting a 10-fold interpenetrating diamondoid network with unprecedented [5 + 5] mode by Xian-Min Guo; Lun Zhao; Heng-Ye Zou; Yong-Nian Yan; Yan-Juan Qi; Qiang Wang (57-60).
A novel coordination polymer [AgBF4(bocb)2] (1) (bocb = 1,4-bis(4-oxy-1-cyano)benzene) has been synthesized. This compound exhibits a ten-fold diamondoid framework with an unusual [5 + 5] mode of interpenetration. Its luminescent property was also investigated.Display Omitted
Keywords: Coordination polymers; Entanglement; Diamondoid network; [5 + 5] mode;

The chlorides of s2 metal cations including Sn2 +, Sb3 +, Bi3 + and Te4 + form complexes with hypericin as indicated by a blue shift of the absorption and fluorescence of hypericin. It is suggested that this is caused by a stabilization of the aromatic HOMO of hypericin by the s2 metal centers. This, in turn, increases the HOMO/LUMO gap of hypericin. A concomitant decrease of the fluorescence intensity occurs, probably due to a heavy-atom effect.The fluorescence of hypericin undergoes a blue shift upon complexation of hypericin by s2 metal ions.Display Omitted
Keywords: Fluorescence; Hypericin; s2 Metal ions;

A 3D In(III) metal organic framework {[(CH3)2NH2][In2(Ox)3.5(Im)]∙H2O∙DMF}n (1) (Ox = oxalic acid, Im = imidazole) which is templated by imidazole molecules has been synthesized solvothermally. Compound 1, is an anionic framework with 1D open channels which are filled with (CH3)2NH2 +, DMF and water molecules. The network exhibits a 3,4-c binodal net with a rare tcj/hc topology. The total solvent accessible volume in the crystal is 43.2%. Sorption studies show that it can adsorb a maximum amount of 47 cm3  g− 1 of CO2 gas at 195 K while the uptake of N2 and CH4 is negligible.A novel indium-oxalate based 3D porous MOF is synthesized which is templated by imidazole molecules. The resulted MOF has 1D continuous channels which are filled with solvent molecules. Gas sorption studies revealed that it can uptake an amount of 47 cm3  g− 1 of CO2 gas at 195 K.Display Omitted
Keywords: Solvothermal; Indium (III); Metal–organic framework; Sorption; Topology;

Design and synthesis of a novel d 10d 10 mixed metal-based polymer with superior luminescent properties to select Ca2 + and Zn2 + by Jie Qu; Wen Gu; Paul R. Coxon; Mike Coto; Xin Liu; Kai Xi; Ningyi Yuan; Jianning Ding (66-68).
A novel luminescent probe based on Ag–Cu mixed metal coordination polymer has been designed and synthesized. Luminescent experiment indicates two peaks with maxima near 425 (Ag) and 660 nm (Cu), which shows high selectivity to Ca2 + and Zn2 +.A novel luminescent probe based on Ag–Cu mixed metal coordination polymer has been designed and synthesized, which shows high selectivity to Ca2 + and Zn2 +.Display Omitted
Keywords: d 10 mixed-metal; Polymer; Luminescent properties; High-performance selectivity;

From reactions of [M2(CO)8(MeCN)2] (M=Mn, Re) with 2-mercaptobenzoxazol, trinuclear clusters [Mn3(CO)10(μ-SCNOC6H4)3] and [Re3(CO)12(μ-SCNOC6H4)3] have been isolated; the former contains 2-mercaptobenzoxazolate ligands in three different binding modes, while in the latter all three bridge rhenium centres by S,N-coordination, but the three rhenium atoms all have different coordination environments.Reactions of [M2(CO)8(MeCN)2] (M=Mn, Re) with 2-mercaptobenzoxazol afford 54-electron trinuclear clusters [Mn3(CO)10(μ-SCNOC6H4)3] and [Re3(CO)12(μ-SCNOC6H4)3]; the former contains 2-mercaptobenzoxazolate ligands in three different binding modes, while in the latter all three bridge rhenium centres by S,N-coordination, but the three rhenium atoms all have different coordination environments.Display Omitted
Keywords: 2-Mercaptobenzoxazolate; Trinuclear macrocyclic clusters; Binding modes; X-ray diffraction;

A colorimetric Schiff base chemosensor for CN by naked-eye in aqueous solution by Hyun Yong Jo; Seul Ah. Lee; Yu Jeong Na; Gyeong Jin Park; Cheal Kim (73-76).
A highly selective colorimetric chemosensor 6,6′-((1E,1′E)-hydrazine-1,2-diylidenebis(methanylylidene))bis(2,4-dichlorophenol) (1) based on the combination of hydrazine and 3,5-dichloro-2-hydroxybenzaldehyde was designed and synthesized. Receptor 1 showed exclusive response toward cyanide by a color change from colorless to yellow in aqueous solution. The binding mode of 1-CN species was determined to be a 1:1 stoichiometry through Job plot, 1H NMR titration, and ESI-mass spectrometry analysis. Also, the sensor 1 could be recyclable simply through treatment with a proper reagent such as hydrochloric acid.A highly selective colorimetric chemosensor (1) based on the combination of hydrazine and 3,5-dichloro-2-hydroxybenzaldehyde was designed and synthesized. Receptor 1 showed exclusive response toward cyanide by a color change from colorless to yellow in aqueous solution. The binding mode of 1-CN species was determined to be a 1:1 stoichiometry through Job plot, 1H NMR titration, and ESI-mass spectrometry analysis.Display Omitted
Keywords: Deprotonation cyanide; Colorimetric; Schiff base; Reversible;

A new microporous metal–organic framework, [Cd(bpdc)0.5(atz)(DMF)]·0.5DMF (1) (H2bpdc = 4,4′-biphenyldicarboxylic acid, Hatz = 3-amino-1,2,4-triazole, DMF = N,N-dimethylformamide) has been solvothermally synthesized by employing the mixed H2bpdc and Hatz ligands. 1 is a 3D pillared-layer framework, consisting of Cd–triazolate layer and dicarboxylate pillar, which exhibits a 6-connected (46  · 68  · 8) self-penetrating net. Because of the pore system functionalized by amino groups and open metal sites, this material shows high CO2 adsorption selectivity over H2 and N2. In addition, 1 exhibits blue emission at ambient temperature.A new self-penetrating amine-decorated microporous metal–organic framework has been constructed by employing the mixed ligands strategy, displaying adsorption selectivity and luminescence properties.Display Omitted
Keywords: Metal–organic framework; Self-penetrating; Sorption; Luminescence;

The hexanuclear compound [Cu4Gd2(H2L)4(NO3)4(H2O)3](NO3)2·5.5H2O·CH3COOH (1) (where H2L = C17H16N2O4 is the dianion of the N,N′-bis(2,3-dihydroxybenzylidene)-1,3-diaminopropane) crystallizes in the triclinic system, space group P  − 1. The hexanuclear cationic moiety is built up by two heterotrinuclear [CuII 2GdIII] units linked by a nitrato group that bridges two copper(II) ions. Magnetic analysis reveals ferromagnetic interactions between metal centers within the cluster with J CuGd equal to 9.9(3) cm− 1.The synthesis, structure and magnetic properties of the novel hexanuclear cluster [Cu4Gd2(H2L)4(NO3)4(H2O)3](NO3)2·5.5H2O·CH3COOH (1) were described. The compound was obtained by connecting heterotriniclear [CuII 2GdIII] units with nitrato linkers. Magnetic analysis reveals ferromagnetic interactions between metal centers within the cluster with J value equal to J Cu–Gd  = 9.9(3) cm− 1.Display Omitted
Keywords: Hexanuclear complex; 3d–4f compound; Ferromagnetic interaction; Schiff base; Copper–gadolinium complex;

The synthesis and magnetic properties of two tetranuclear Ni complex Ni4(L)4(CH3CN)4(OCH3)4 1 and Co complex Co4(L)4(CH3CN)4(OCH3)4 2 (HL = 2-mercaptobenzoxazole) are reported. The X-ray structures reveal that 1 and 2 are isostructural with [Ni4O4] 1 and [Co4O4] 2 cubane-like cores. Analysis of the temperature dependent magnetic measurements data shows that both complexes are paramagnetic with weak antiferromagnetic coupling. One-J model and two-J model are both applied to fit the experimental magnetic data of 1 and the results indicate the exchange coupling between the type A Ni(II) ions affected by NCS three atoms bridge in 2-mercaptobenzoxazole ligand.The synthesis and magnetic properties of two tetranuclear Ni complex Ni4(L)4(CH3CN)4(OCH3)4 1 and Co complexes Co4(L)4(CH3CN)4(OCH3)4 2 (HL = 2-mercaptobenzoxazole).Display Omitted
Keywords: Tetranuclear Ni(II); Tetranuclear Co(II); Crystal structure; Magnetic properties; Cubane core;

Luminescent properties of 4,4-bipyridinium chlorobismuthate salt: Strong influence of solvation by Sergey A. Adonin; Maxim N. Sokolov; Marianna E. Rakhmanova; Anton I. Smolentsev; Ilya V. Korolkov; Svetlana G. Kozlova; Vladimir P. Fedin (89-91).
Reaction of BiCl3 and 4,4-bipy in 2 M HCl leads to the formation of 4,4-bipyridinium salt of binuclear chlorobismuthate complex (bipyH2)2[Bi2Cl10]·2H2O (1). When heated in air, 1 loses the solvate water molecules to give (bipyH2)2[Bi2Cl10] (2). The dehydration results in significant changes in luminescent behavior.The luminescent behavior of binuclear chlorobismuthate complex (bipyH2)2[Bi2Cl10]·2H2O (1) changes significantly when dried in air to form non-aqueous (bipyH2)2[Bi2Cl10] (2). Experimental data are confirmed by electronic structure calculations.Display Omitted
Keywords: Chlorobismuthate; Bismuth; Solvate; Luminescence;

Circular dichroism enhancement by the coordination of different metal ions with a pair of chiral tripodal ligands by Hai-Ping Wang; Shao-Yun Yin; Mei Pan; Kai Wu; Ling Chen; Yi-Xuan Zhu; Ya-Jun Hou (92-95).
The coordination of metal ions with a pair of chiral tripodal ligands (R or S)-2-(2-((bis(pyridin-2-ylmethyl)amino)methyl)phenoxy)-N-(1-phenylethyl)acetamide (R- or S-L) results in the circular dichroism (CD) enhancement distinctly, giving fingerprint information among different metals. Specifically, the CD signals show more obvious magnification upon coordination with Ln3 + compared with Zn2 + and other metals. Structural analyses show that in Eu-complex (1), the Eu3 + metal center is surrounded in a 10-coordinating geometry and the ligand takes fan-like configuration, while in Zn-complex (2), Zn2 + is surrounded in a 7-coordinating geometry and the ligand takes pincer-like configuration. These differences in the coordination structure as well as intramolecular packing effects are responsible for the variation in CD signal responses of different metal-coordinated systems.The coordination of different metal ions with a pair of chiral tripodal ligands results in discriminatively magnified CD signal responses, which can be applied as a potential CD “switch” or “regulator”.Display Omitted
Keywords: Circular dichroism; Metal coordination;

(Ferrocenylthienyl)phosphines for the Suzuki–Miyaura C,C coupling by Christian Gäbler; Marcus Korb; Dieter Schaarschmidt; J. Matthäus Speck; Alexander Hildebrandt; Heinrich Lang (96-99).
2-(3-Ferrocenylthienyl)phosphines of type 2-PR2-3-Fc- c C4H2S (R =  t Bu (2); R = Ph (3); Fc = Fe(η 5-C5H4)(η 5-C5H5)) were synthesized and the structures of 2 and 3 in the solid state were determined by single X-ray structure analysis. Inter- and intra-molecular T-shaped π⋯π stackings involving cyclopentadienyl and phenyl rings are characteristic for 3. The application of 2 and 3 as ligands in the Pd-catalyzed Suzuki–Miyaura C,C cross-coupling of aryl halides with boronic acids to give the respective biaryls is reported. Electron-rich, electron-poor and sterically hindered substrates could be coupled with high yields at Pd-loadings as low as 0.1 mol%.2-(3-Ferrocenylthienyl)phosphines were synthesized and their application as ligands in the Pd-catalyzed Suzuki–Miyaura C,C cross-coupling of aryl halides with boronic acids to give the respective biaryls is reported. Electron-rich, electron-poor as well as sterically hindered substrates could be coupled with high yields at Pd-loadings as low as 0.1 mol%.Display Omitted
Keywords: Suzuki–Miyaura; C,C coupling; Phosphine thiophenes; Homogenous catalysis; Solid state structure;