Inorganic Chemistry Communications (v.66, #C)

Contents List (iii-viii).

Synthesis, characterization, and application for addition polymerization of norbornene of novel acetylacetonate bis(anilines) palladium (II) complexes by D.S. Suslov; M.V. Bykov; P.A. Abramov; M.V. Pakhomova; I.A. Ushakov; V.K. Voronov; V.S. Tkach (1-4).
New acetylacetonate bis(aniline) palladium (II) complexes were synthesized by nitrile substitution of [Pd(acac)(MeCN)2]BF4 with L (L =  o-toluidine, p-toluidine, 2,6-dimethylaniline, 2,6-diisopropylaniline) which yielded [Pd(acac)(L)2]BF4 as a mononuclear species with chelating acac ligand. Preliminary investigations into the polymerization of norbornene in the presence of BF3·OEt2 were performed. An X-ray diffraction study of [Pd(acac){NH2(2,6-Me2C6H3)}2]BF4 establishes the presence of hydrogen bonding between the 2,6-dimethylaniline ligand and [BF4] anion.Display Omitted
Keywords: Palladium; Norbornene; Polymerization; Anilines;

Two zinc porphyrin based dyads, 5, 10, 15, 20-tetra-4-(2-(10H-phenothiazin-10-yl)ethoxy)phenyl porphyrinato zinc (II) and 5,10,15,20-tetra-4-(bis(4′-tert-butylbiphenyl-4-yl)amino)phenyl porphyrinato zinc(II) containing four phenothiazine or bis(4′-tert-butylbiphenyl-4-yl)aniline moieties tethered to porphyrin framework were synthesized, and systematically characterized using 1H NMR, mass, UV–visible and steady state fluorescence techniques. Excitation of 5,10,15,20-tetra-4-(bis(4′-tert-butylbiphenyl-4-yl)amino)phenyl porphyrinato zinc(II) at 335 nm, resulted in quenched emission of bis(4′-tert-butylbiphenyl-4-yl)aniline moiety, when compared to pristine bis(4′-tert-butylbiphenyl-4-yl)aniline, and appearance of porphyrin emission at 618 nm, due to intramolecular energy transfer from bis(4′-tert-butylbiphenyl-4-yl)aniline moiety to porphyrin. The porphyrin dyads were titrated with phenylimidazole appended fullerenes, N-Methyl-4-(1H-imidazol-1-yl)phenylfullero[C60]pyrrolidine or N-Methyl-4-(1H-imidazol-1-yl)phenylfullero[C70]pyrrolidine and supramolecular triads of the type, (PTZ or BBA)4-ZnP:(C60Im or C70Im) were formed in which, zinc porphyrin and fullerenes act as primary electron donor and acceptors, while phenothiazine or bis(4′-tert-butylbiphenyl-4-yl)aniline moieties behave as secondary electron donors in photo-induced electron transfer events. Optical absorption and 1H NMR titration studies confirmed the formation of supramolecular triads and the steady state fluorescence experiments revealed the quenching of porphyrin emission upon addition of increasing amounts of N-Methyl-4-(1H-imidazol-1-yl)phenylfullero[C60]pyrrolidine or N-Methyl-4-(1H-imidazol-1-yl)phenylfullero[C70]pyrrolidine indicating the occurrence of photo-induced electron transfer from 1ZnP to co-ordinated fullerene moieties.Display Omitted
Keywords: Porphyrin; Fullero[C60,C70]pyrrolidine; Photo-induced electron transfer; Energy transfer;

First coordination polymers on the bases of chiral thiophosphorylated thioureas by Kirill E. Metlushka; Dilyara N. Sadkova; Liliya N. Shaimardanova; Kristina A. Nikitina; Kamil A. Ivshin; Daut R. Islamov; Olga N. Kataeva; Alexey V. Alfonsov; Vladislav E. Kataev; Alexandra D. Voloshina; Ludmila N. Punegova; Vladimir A. Alfonsov (11-14).
The preparation and structure of the new coordination polymers [NiL2pz]n (HL = (rac)-, (R)- or (S)-PhCH(CH3)NHC(S)NHP(S)(OEt)2) were described. The preliminary biological test revealed high activity of the complexes towards Staphilococcus aureus and Bacillus cereus.The preparation and structure of the new coordination polymers [NiL2pz]n (HL = (rac)-, (R)- or (S)-PhCH(CH3)NHC(S)NHP(S)(OEt)2) were described. The preliminary biological test revealed high activity of the complexes towards Staphilococcus aureus and Bacillus cereus.Display Omitted
Keywords: Chiral coordination polymers; Thiophosphorylated thioureas; Biological activity; Magnetic properties;

A series of half-sandwich ruthenium(II) complexes containing Schiff-base ligands [Ru(p-cymene)LCl] [HL = (E)-4-X-2-((phenylimino)methyl)phenol, X = H (2a); X = CH3 (2b); X = Cl (2c) and X = Br (2d)] have been synthesized and fully characterized by 1H and 13C NMR spectra, elemental analyses and infrared spectrometry. Moreover, the molecular structures of ruthenium complexes 2b and 2c were confirmed by single-crystal X-ray diffraction methods. These half-sandwich ruthenium complexes are highly catalyzed hydrogenation of nitroarenes to aromatic anilines to proceed in the presence of sodium borohydride reducing agent in ethanol solvent. Notably, complex 2c was found to be a very efficient catalyst toward reduction of nitroarene compounds with wide functional group compatibility and substrate scope.Half-sandwich ruthenium(II) complex containing Schiff-base ligand was found to be a very efficient catalyst toward reduction of nitroarenes reaction in the presence of sodium borohydride in ethanol solvent.Display Omitted
Keywords: Ruthenium; Complex; Structure; Nitroarene; Reduction;

Three new coordination polymers, namely, {[Cu2(IPT)(SO4)(OH)(H2O)]·H2O}n (HIPT = 5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd2(IPT)(NPA)(OH)]·H2O}n (H2NPA = 5-nitroisophthalic acid, 2), and {[Zn2(IPT)(IDC)(H2O)]·3H2O} n (H3IDC = 1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu2(IPT)(SO4)(OH)]n secondary building blocks and IPT linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA2 − pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]n chains and binuclear Zn2(IPT)2 rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature.Three new CPs with interesting structures based on a bifunctional ligand containing both imidazole and tetrazole groups were constructed. Their diverse structures and luminescent properties were studied.Display Omitted
Keywords: 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate; Coordination polymer; Solid-state luminescent;

A novel two-dimensional (2-D) solid material [Ni(en)2]2{SiMoVI 8VIV 6O42[Ni(en)2]2}·4H2O 1 (en = ethylenediamine) has been hydrothermally synthesized and structurally characterized by IR, UV–Vis spectrum, elemental analysis, XRD, ESR, XPS, X-ray diffraction analysis, magnetic property analysis and electrochemistry study. Single-crystal X-ray analysis reveals that the 2-D framework of compound 1 is based on Mo/V/Si bicapped Keggin clusters interconnected by nickel ethylenediamine complexes. Magnetic susceptibility measurement indicates that compound 1 exhibits antiferromagnetic coupling interactions.A novel two-dimensional (2-D) solid material [Ni(en)2]2{SiMoVI 8VIV 6O42[Ni(en)2]2}·4H2O 1 (en = ethylenediamine) has been hydrothermally synthesized and characterized.Display Omitted
Keywords: Polyoxometalates; Hydrothermal synthesis; Magnetic property; Crystal structure;

Hexachloroplatinate(IV) anion-induced cucurbit[5]uril and cucurbit[8]uril supramolecular assemblies with linear channels by Xue-Tong Zhu; Ning-Ning Ji; Yun-Qian Zhang; Sai-Feng Xue; Zhu Tao; Qian-Jiang Zhu (28-32).
Two Q[n]-based porous compounds, Q[5]·[PtCl6]2 −·2H3O·12H2O and 2Q[8]·[PtCl6]2 −·2H3O·74H2O in cooperating the hexachloroplatinate(IV) anion ([PtCl6]2 −) as an inorganic structure directing agent are demonstrated. The driving forces for the formation of such novel Q[n]-based porous compounds are considered to be the outer surface interactions of Q[n]s, including dipole interactions between Q[n]s and ion-dipole interactions between [PtCl6]2 − anions and Q[n]s. Moreover, the Q[5]-based porous compound displays absorption distinctness for tetrachloromethane, whereas the Q[8]-based porous compound displays absorption distinctness for methanol.Two Q[n]-based porous compounds, Q[5]·[PtCl6]2 −·2H3O·12H2O and 2Q[8]·[PtCl6]2 −·2H3O·74H2O in cooperating the hexachloroplatinate(IV) anion ([PtCl6]2 −) as an inorganic structure inducer are demonstrated. The Q[5]·[PtCl6]2 −·2H3O·12H2O and 2Q[8]·[PtCl6]2 ·2H3O·74H2O have permanent porosity may potentially be useful for gas storage, Moreover, the Q[5]-based porous compound displays selective absorption of tetrachloromethane, whereas the Q[8]-based porous compound displays selective absorption of methanol.Display Omitted
Keywords: Cucurbit[n]urils; Hexachloroplatinate anion; Porous compounds; Supramolecular; Assemblies; Absorption;

Preparation, characterization and electrical properties of Ca and Sr doped LaCrO3 by Hui Qi; Yongxin Luan; Songtian Che; Ling Zuo; Xudong Zhao; Changmin Hou (33-35).
Perovskite structure chromites are one of the most important family of functional materials, especially useful as interconnect materials in solid oxide fuel cells (SOFCs). In this paper, the relationship of the structure, valence states of Cr, and electrical conductivity of La0.8Ca0.2CrO3 and La0.7Ca0.2Sr0.1CrO3 were studied. The samples were synthesized by solid state reaction under air or nitrogen condition, respectively. It is found that the relationship of AC conductivity with frequency is in consistent with Jonscher power law when the frequency is between 2 × 102–2 × 106  Hz. The electrical resistivity is in line with temperature change, which means that the conduction mechanism is small polaron theory and meets Arrhenius formula. Binding energy of the Cr2p in the compounds synthesized in air corresponded to 576.4 eV, 577.6 eV and 579.7 eV, which means the valence states of Cr are + 3, + 5 and + 6. But for the compounds synthesized in N2 atmosphere the valence states of Cr are + 3 and + 6.In this paper, the relationship of the structure, valence states of Cr, and electrical conductivity of La0.8Ca0.2CrO3 and La0.7Ca0.2Sr0.1CrO3 were studied.Display Omitted
Keywords: Doped-LaCrO3; Valence states; Conductivity;

A series of new metal–organic frameworks (MOFs) composed of a transition-metal organic acid salt and 2, 5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene (3-bpdh) was prepared via diffusion in a H2O–MeOH solvent system. The results illustrated that MOFs self-assembly should be achieved by metal-ion potential and building blocks. The loading of MOF microcrystals with titanium dioxide resulted in the composite photocatalyst TiO2@ZnMOF, which exhibited excellent photodegradation (64%) of the dye methyl blue. Importantly, this approach provides an innovative way of enhancing the photocatalytic effect of MOFs with potential applications as a catalyst support.A series of new metal–organic frameworks (MOFs) composed of a transition-metal organic acid salt and 2, 5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene (3-bpdh) was achieved by metal-ion potential and building blocks. The loading of MOF microcrystals with titanium dioxide exhibited excellent photodegradation of the dye methyl blue.Display Omitted
Keywords: Metal–organic frameworks; Metal-ion potential; Building blocks; Micro-nanocrystals; Composite photocatalyst;

Two three dimensional (3D) Co(II) coordination polymers incorporating similar substituted imidazole-dicarboxylate and dipyridyl-type ancillary ligands pillared layer, namely, {Co3(mimda3 −)2 (bpe)3·3H2O}n (1) and {Co3 (eimda3 −)2(bipy)3·8H2O}n (2) (H3mimda = 1H-2-methyl-4,5-imidazole-dicarboxylic acid, while H3eimda = 1H-2-ethyl-4,5-imidazole-dicarboxylic acid, bpe = 1,2-di(4-pyridyl) ethylene and bipy = 4, 4′-bipyridine) have been successfully synthesized. Both polymers 1 and 2 have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, and thermogravimetric analysis (TGA). X-ray structural analysis reveals that they are nearly isostructural, possessing similar symmetry units based on trinuclear clusters, and further is propagated into a Kagomé-like lattice. The lattice consists of corner-sharing triangles of spins with magnetic coupling between the nearest neighboring Co(II) ions. Magnetic measurements revealed spin-canting-like antiferromagnetism behaviors for compounds 1 and 2 at lower temperature. The interaction in 1 is slightly stronger than that of 2, which can be explained by the discrepancy of organic linker between the adjacent Co(II) centers.Two three dimensional (3D) Co(II) coordination polymers incorporating similar substituted imidazole-dicarboxylate and dipyridyl-type ancillary ligands pillared layer have been successfully afforded. X-ray structural analysis reveals that they are nearly isostructural and magnetic measurements revealed spin-canting-like antiferromagnetism behaviors at lower temperature.We show a mixed ligands approach used in a promising way to construct new molecular magnetic materials.Display Omitted
Keywords: Substituted imidazole-dicarboxylate; Single X-ray analysis; Trinuclear cluster; Antiferromagnetic exchange; Spin-canting;

Frequently used, but still unknown: Terbium(III) tris-hexafluoroacetylacetonate dihydrate by Irina Yu. Bagryanskaya; Larisa V. Politanskaya; Evgeny V. Tretyakov (47-50).
This work provides direct access to the complex [Tb(hfa)3(H2O)2] with elucidation of the molecular and crystal structure. It has been shown that the interaction of Tb(OAc)3·4H2O with H-hfa·2H2O in water gives {[Tb2(hfa)4(F3CCO2)2(H2O)4][Tb(hfa)3(H2O)2]2·H2O}, which can be used as a source of pure [Tb(hfa)3(H2O)2]. This compound is a good quantitative precursor for the synthesis of various Tb(hfa)3 complexes due to its good solubility in common organic solvents such as hexane, benzene, ether and acetone. Hence, it opens new possibilities in the field of molecular magnetism and design for photonic and optoelectronic applications.The synthesis, molecular and crystal structures of terbium(III) tris-hexafluoroacetylacetonate dihydrate, synthesised as a key precursor to single-molecular based magnets, are reported.Display Omitted
Keywords: Crystal structure; Terbium hexafluoroacetylacetonate; Lanthanide β-diketonates; Single-molecule magnet materials;

Two new coordination polymers, {[Cd(BIDPT)(oba)]·0.5H2O} n (1) and {[Zn(BIDPT)(4,4′-sdb)]·2.25H2O} n (2) (BIDPT = 4,4′-bis(imidazol-l-yl)diphenyl thioether, H2oba = 4,4′-oxydibenzoic acid, 4,4′-H2sdb = 4,4′-sulfonyldibenzoic acid), have been solvothermally synthesized and characterized. Both 1 and 2 show 2-fold interpenetrating 3D frameworks with {65  ∙ 8} cds and {66} dia topology, respectively. These two coordination polymers show strong luminescence and their luminescence could be quenched by a series of nitro explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitro explosives.Two new 2-fold interpenetrating Cd/Zn metal–organic frameworks show strong luminescence and their luminescence could be quenched by a series of nitroaromatic explosives. They exhibit very highly sensitive and selective detection of picric acid compared to other nitroaromatic explosives.Display Omitted
Keywords: Coordination polymer; Crystal structure; Nitro explosives; Syntheses;

Coexistence of the single chain magnet and spin-glass behavior in a cyano-bridged {FeIII 2FeII} chain by Liang Zhao; Yan-Juan Zhang; Ji-Xiang Hu; Cheng-Qi Jiao; Jun-Li Wang; Chun-Ying Duan; Tao Liu (55-58).
A cyano-bridged ferromagnetic {FeIII 2FeII} alternating chain {[FeIII(pzTp)(CN)3]2[FeII(imidazole)(H2O)]}·3H2O (1) (pzTp = tetrakis(pyrazolyl)borate) was synthesized via rational design. Crystal structure analysis studies demonstrated that complex 1 had a one-dimensional double zigzagging chain-like structure. Magnetic measurements showed that ferromagnetic interactions dominate in 1 and the AC magnetic susceptibility revealed two limit regimes in accordance with the single chain magnet and spin-glass behavior.One cyano-bridged based {FeIII 2FeII} chain has been synthesized by utilizing the thricyanometallate precursors [FeIII(pzTp)(CN)3] with the Fe2 + ion and imidazole as an auxiliary ligand. The complex exhibits the coexistence of the single chain magnet and spin-glass behavior.Display Omitted
Keywords: Cyano-bridged; Single chain magnet; Spin-glass;

A new series of lanthanide metal complexes [Ln(L)3]n (L = p-methoxybenzoic acid, Ln = Pr 1, Eu 2, Tb 3, Dy 4, Ho 5, Er 6, Yb 7) have been synthesized under hydrothermal conditions. Single-crystal X-ray diffraction measurements reveal that these compounds are isostructural, crystallizing in the monoclinic space group P21/c and giving 1D chain structures. Magnetic studies reveal antiferromagnetic behavior for complexes 1, 3, 5 and 6, ferromagnetic behavior for complex 4 and spin-canting behavior for 7.A new series of lanthanide metal complexes have been synthesized and characterized. These compounds are isostructural, crystallizing in the monoclinic space group P21/c and giving 1D chain structures. Magnetic studies reveal antiferromagnetic behavior for complexes 1, 3, 5 and 6, ferromagnetic behavior for complex 4 and spin-canting behavior for 7.Display Omitted
Keywords: Crystal structures; Lanthanide complexes; Solvothermal synthesis; Magnetic properties;

Mixed-node A-Cu-BTC (A = Sr, La, Ce, Al) was obtained through hydrothermal method, which was already successfully investigated that could be applied as a catalyst in selective catalytic reduction of NO with CO (CO-SCR). Mixed-node A atoms were proved through elemental analysis method using an Energy Dispersive Spectrometer. In addition, CuOy/C and AOx/CuOy/C were obtained by a heat treatment of A-Cu-BTC under N2 atmosphere, which were found to be more effective as lower temperature catalysts. These characterizations of mixed-node A-Cu-BTC and AOx/CuOy/C were performed by scanning electron microscopy with energy dispersive X-ray analysis, X-ray powder diffraction, infrared spectroscopy, thermo-gravimetric analysis and specific surface area using the BET method. The possible reaction mechanism about CO-SCR is discussed. These results provide that mixed-node MOFs and oxides prepared from mixed-node MOFs both have a promising application for CO-SCR.Series of mixed-node A-Cu-BTC catalysts were obtained through solvothermal method, investigating that could be as promising selective catalytic reduction with NO by CO. AOx/CuOy/C were also obtained and investigated in CO–NO reaction, which were successfully applied in a lower catalytic temperature.Display Omitted
Keywords: Cu-BTC; MOF precursor; Carbon based catalyst; Selective catalytic reduction;

By combining experiment with molecular simulation, the CO2 sorption performance of a 2D honeycomb layered coordination polymer, {[Zn2(bpydb)2(H2O)2](DMA)3(H2O)}n (1) (bpydb = 4,4′-(4,4′-bipyridine-2,6-diyl) dibenzoate) was systematically investigated. The desolvated 1 not only shows high CO2 capacity (72.5 cm3/g at 273 K and 42.9 cm3/g at 298 K) with a moderate high zero-coverage adsorption enthalpy (29.7 kJ/mol), but also exhibits excellent CO2/N2 selectivity around room temperature. To better understand the adsorption behaviors and adsorption sites for CO2 in 1, GCMC simulations were carried out, which indicate that the open metal sites between two adjacent layers account for the high CO2 sorption capacity and strong CO2 binding ability. Moreover, the thermal stability of 1 was further confirmed by the TGA and VT-PXRD, which indicate that 1 could be thermally stable up to 400 °C.The gas sorption behaviors of a Zn(II) 2D layered coordination polymer was investigated both experimentally and theoretically. The relevant results show that the coordination polymer possesses high CO2 sorption ability and CO2/N2 separation performance, which, from the GCMC simulation results, should be attributed to the open metal sites along with the suitable pore surroundings contribute.Display Omitted
Keywords: Coordination polymer; Thermal stability; CO2 adsorption; GCMC simulation;

Synthesis, isolation and characterization of dinuclear oxidodiiron(III) complexes modified by monodentate pyridines by Michael Haberberger; Kerstin Mayer; Elisabeth Irran; Robert Kretschmer; Stephan Enthaler (73-78).
In the present study, iron complexes modified by differently substituted monodentate pyridine ligands containing a [Fe–O–Fe] unit have been synthesized, isolated and characterized. Noteworthy, the complexes are easily accessible by the reaction of pyridines with iron(II) chloride in the presence of molecular oxygen, which is the source for the oxido bridge as proven by labelling experiments. Interestingly, in dependency of the electronic and steric properties of the applied ligand different geometries have been observed by X-ray diffraction analysis. On one hand with pyridine or 4-dimethylaminopyridine as ligand (L) a L4ClFe–O–FeCl3 motif was accessible, while with 4-tert-butylpyridine a L2Cl2Fe–O–FeCl2L2 motif was realized. With the aid of Mößbauer spectroscopy an oxidation state + III was assigned for all iron centres. Moreover, the complexes were easily converted by addition of silver benzoate to trinuclear complexes with a [Fe3O] core.Display Omitted
Keywords: Iron complex; Oxygen activation; Coordination chemistry; Binuclear complex;

An unusual 8-connected self-penetrating metal–organic framework based on binuclear cadmium clusters by Xianmin Guo; Helong Bai; Huadong Guo; Yongnian Yan; Yanjuan Qi (79-82).
A novel metal–organic framework based on binuclear cadmium clusters has been synthesized and characterized, which represents a new kind of 8-connected uninodal network topology presently known for self-penetrating systems.A novel metal–organic framework, [Cd2(cdc)2(ibpi)2]·2H2O (1) (ibpi = 1-(4-(4-(1H-imidazol-1-yl)benzyloxy)phenyl)-1H-imidazole, and H2cdc = 1,4-cyclohexanedicarboxylic acid), has been synthesized and structurally characterized. This compound represents an unusual 8-connected uninodal network topology presently known for self-penetrating systems.Display Omitted
Keywords: Metal–organic framework; 8-Connected; Self-penetration; Luminescence;

KMg6(P2O7)2P3O10: A novel phosphate with two distinct anions by Yaoguo Shen; Siyuan Zeng; Yingying Xu; Sijie Liu; Sasa Wang; Zhenyue Wu; Sangen Zhao; Junhua Luo (83-86).
A novel mixed-anion phosphate, KMg6(P2O7)2P3O10, has been synthesized by spontaneous crystallization technique with K2O–P2O5–Li2O as a flux. Single-crystal X-ray analysis reveals that KMg6(P2O7)2P3O10 features two kinds of isolated anions, [P2O7] dimers and [P3O10] trimers. Such coexisting of two distinct anions in one polyphosphate, which has somewhat conflict with Pauling's parsimony (V) rule, is very rare in alkali metal and alkali-earth metal phosphates. This finding enriches the structural chemistry of phosphates and provides new perspective on the design of multiple anion materials. The thermal stability and a.c. conductivity of KMg6(P2O7)2P3O10 are also discussed in this paper.Two kinds of isolated polyphosphate anions, [P2O7] clusters and [P3O10] clusters, coexist in the phosphate KMg6(P2O7)2P3O10, which crystallizes in the monoclinic space group P21/m. Such coexisting of two distinct anions in one polyphosphate, which has somewhat conflict with Pauling's parsimony (V) rule, is very rare in alkali metal and alkali-earth metal phosphates. Discovery of this compound enriches the structural chemistry of phosphates and may provide new perspective on the design of multiple anion materials.Display Omitted
Keywords: Mixed-anion phosphate; Pauling's parsimony rule; Infrared spectrum;

A pillar-layer MOF used as a luminescent probe for detecting small molecules acetone by Bao-Li Li; Hai-Ning Wang; Liang Zhao; Guang-Zhe Li; Zhong-Min Su (87-89).
The reactions of 4,4-bipyridine and 5-Hydroxyisophthalic acid with Zn(NO3)2·3H2O in N,N′-dimethylacetamide lead to the formation of [Zn(5-hip)(bpy)]·2DMA (1). Compound 1 possesses a non-interpenetrating pillar-layer framework with 1D rectangular-shape channels. The experimental results show that the luminescent intensity of 1 highly depends on small solvent molecules, particularly CH3OH and acetone. Compound 1 can be used as a luminescent probe to detect small molecule acetone.The reactions of 4,4-bipyridine and 5-Hydroxyisophthalic acid with Zn(NO3)2·3H2O in N,N′-dimethylacetamide lead to the formation of [Zn(5-hip)(bpy)]·2DMA (1). Compound 1 can be used as a luminescent probe to detect small molecule acetone. The results show that the luminescent intensity of 1 highly depends on small molecule acetone. The luminescent intensity decreases gradually with the increase of amounts of acetone.Display Omitted
Keywords: Metal–organic frameworks; Luminescence; Sensing;

Redox-induced linkage isomerization detected in [Ru(NH3)5(NVF)](PF6)2(NVF =  N-vinylformamide) by Gaston Pourrieux; Pedro O. Abate; Mónica M. Vergara; Néstor E. Katz (90-93).
A new ruthenium (II) complex, of formula [Ru(NH3)5(NVF)](PF6)2, 1 (with NVF =  N-vinylformamide) was synthesized and characterized by chemical analyses, spectroscopic and electrochemical techniques. The presence of two coordination sites within NVF makes complex 1 capable of showing a redox-dependent linkage isomerization process, which was detected by cyclic voltammetry and spectroelectrochemical measurements. Upon oxidation of the metallic center from Ru (II) to Ru (III) of complex 1 in N,N-dimethylformamide, linkage isomerization takes place from a vinyl-coordinated Ru(II) to an amide-coordinated Ru(III). This is an additional example of a system that can be applied in molecular memory devices or engines of a molecular machine.A pentaammineruthenium(II) complex with N-vinylformide presents a redox-induced linkage isomerization process from a vinyl-coordinated Ru(II) to an amide-coordinated Ru(III).Display Omitted
Keywords: Ruthenium; Linkage Isomerization; Molecular Hysteresis;

New bis-o-iminosemiquinonate aluminium(III) complexes by Alexandr V. Piskunov; Irina V. Ershova; Artem S. Bogomyakov; Georgy K. Fukin (94-97).
The first aluminium(III) complexes based on sterically hindered 4,6-di-tert-butyl-N-(2,6-di-iso-propyl-phenyl)-o-iminobenzoquinone (imQ) of general formula imSQ2AlR (where imSQ — is a radical anion of imQ, R = I (1), NCS (2) and N3 (3)) were synthesized. Compounds 13 demonstrate biradical X-band EPR spectra in frozen toluene matrix. The crystalline samples of 13 were characterized using magnetic susceptibility measurements. The antiferromagnetic coupling between spins of o-iminosemiquinonate radicals in 13 is predominant and, as the result, the singlet ground state for pentacoordinated biradical compounds is observed. The molecular structures of all the complexes obtained have been established by the single crystal X-ray analysis.The first aluminium(III) complexes based on sterically hindered o-iminobenzosemiquinone were synthesized. Compounds have a biradical character. The antiferromagnetic coupling between spins of o-iminosemiquinonate radicals is predominant and the singlet ground state for pentacoordinated biradical compounds is observed.Display Omitted
Keywords: o-Iminosemiquinonate; Aluminium; X-ray diffraction; Magnetic susceptibility; EPR spectroscopy;