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'Inorganic Chemistry Communications' ist eine internationale Zeitschrift, die einer raschen Veröffentlichung von Kurzmitteilungen in den wichtigsten Bereichen der anorganischen, metallorganischen und supramolekularen Chemie dient. Die Themen umfassen synthetische Chemie, Kinetik und Mechanismen von Reaktionen, Bioanorganische Chemie, Photochemie und die Verwendung von Metall-und metallorganischen Verbindungen in stöchiometrischen und katalytischen Synthese sowie für organische Synthesen.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Chen-Yu Li, Jing-Kai Su, Chia-Jung Yu, Yu-En Tai, Chia-Her Lin, Bao-Tsan Ko Magnesium catalysts incorporated by sterically bulky benzotriazole-phenoxide ligands (CMe2PhBTP?, t-BuBTP? and TMClBTP?) are synthesized and structurally characterized. The reaction of MgnBu2 with CMe2PhBTP-H (2.0mol Eq) in THF produces penta-coordinated monomeric magnesium complex [(CMe2PhBTP)2Mg(THF)] (1). However, six-coordinated bis-adduct magnesium complexes [(t-BuBTP)2Mg(THF)2] (2) and [(TMClBTP)2 Mg(THF)2] (3) result from treatments of MgnBu2 with t-BuBTP-H and TMClBTP-H in THF under the same stoichiometric proportion, in which each Mg center is coordinated by two THF molecules. Optical properties and catalytic studies for l-lactide polymerizations of magnesium complexes 1–3 are investigated. Magnesium complex 3 catalyzes the ring-opening polymerization effectively not only in a “controlled” fashion but also in an “immortal” manner, giving polymers with the expected molecular weights and narrow molecular weight distributions.
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Magnesium complexes derived from sterically bulky benzotriazole-phenoxide ligands (CMe2PhBTP?, t-BuBTP? and TMClBTP?) were synthesized and fully characterized. Complex 3 is an active catalyst for the ring-opening polymerization of l-lactide in the presence of 9-anthracenemethanol (9-AnOH), giving polymers with expected molecular weights and narrow PDIs.? Magnesium complexes supported by sterically bulky BTP ligands are synthesized and structurally characterized. ? Monomeric Mg complex 1 emits the highest green fluorescence in solution among these complexes. ? Complex 3 catalyzes the polymerization of l-lactide with the “controlled” and “immortal” characters.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Ziya Aydin, Yibin Wei, Maolin Guo A reversible turn-on sensor (Rh–OH–Rh) which can selectively detect Fe3+ in solution has been developed. The sensor combines two rhodamine moieties with a 3-oxygen Fe3+ receptor to provide excellent selectivity for Fe3+ over a range of biologically relevant metal ions. It binds Fe3+ in a 1:1 stoichiometry with an apparent binding constant 5.2×106M?1 (log K=5.28) in ACN/DMF (9/1v/v) solution. The sensor displays distinct “on–off” changes in color and fluorescence upon the alteration of free Fe3+ levels in solution with a reversible response and little interference with other biological relevant metal ions.
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A reversible turn-on sensor (Rh–OH–Rh) which can selectively detect Fe3+ in solution based on distinct “on–off” changes in color and fluorescence has been developed.? A new Fe3+-selective turn-on optical sensor with a 3-oxygen Fe3+ receptor was designed and synthesized. ? The sensor binds Fe3+ in a 1:1 stoichiometry with an apparent binding constant 5.2 × 106 M–1 in solution. ? The sensor displays distinct "on-off" color and fluorescence changes upon the alteration of free Fe3+ levels in solution. ? The sensor has excellent selectivity for Fe3+, with little interference from other metal ions.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Dongdi Zhang, Shaowei Zhang, Pengtao Ma, Jingping Wang, Jingyang Niu The hydrothermal reactions of Keggin-type silicotungstate with rare-earth–transition-metal (RE–TM) heterometals in the presence of mixed ligands of oxalate and en (en = ethylenediamine) generate a novel two-dimensional (2D) organic–inorganic hybrid oxalate-bridging scandium-substituted silicotungstate. The complex [Cu(en)2(H2O)]2{[Cu(en)2(H2O)]2[Cu(en)2]2[(?-SiW11O39)Sc(H2O)]2(C2O4)}·8H2O (1) has been further characterized by elemental analyses, powder X-ray diffraction (PXRD), IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. X-ray structural analysis reveals that 1 exhibits the dimeric mono-Sc substituted Keggin [Sc(?-SiW11O39)]210? subunits linked by the oxalate ligand, which further results in the 2D network architecture interconnected by [Cu(en)2]2+ coordination cations. Notably, 1 represents the first oxalate-bridging RE–TM heterometallic hybrid built by lacunary Keggin silicotungstate-supported RE derivatives and [Cu(en)2]2+ coordination cations. Furthermore, the TG curve of 1 displays two steps of slow weight loss in the range of 25–1000°C.
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The first two-dimensional organic–inorganic hybrid derivative constructed by oxalate-bridging scandium-substituted Keggin-type silicotungstate and [Cu(en)2]2+ coordination cations has been synthesized.? The first oxalate-bridging scandium-substituted Keggin-type silicotungstate. ? The first organic-inorganic hybrid 2D RE-TM heterometallic silicotungstate with the mixed organic ligands. ? The oxalate ligand acts as the tetradentate mode to bind two ScIII cations and two CuII ions, which has not been known.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Angélica Cavalett, Tiago Bortolotto, Patrícia Rabêlo Silva, Gilmar Conte, Hugo Gallardo, Hernán Terenzi This work demonstrates the efficient photocleavage of DNA induced by a terbium complex. Mechanistic studies and DNA groove binding dependence were performed to better understand the photo-cleavage reaction, suggesting the presence of oxygen and carbon-centered radicals in the strand scission event. Furthermore, kinetic analyses were also achieved. The DNA photocleavage promoted by the title complex proceeds with a kobs of ~10.2h?1, a reaction rate useful in molecular biology practices, with a t1/2 of 4min. This complex emerges as a new example of lanthanide compound with DNA cleavage ability by a non-hydrolytic mechanism.
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Great efficiency in DNA cleavage promoted by Tb(tdzp)(acac)3 complex was achieved with UV-light illumination, without significant activity under dark conditions.? The reported complex shows an efficient DNA cleavage activity under UV-A light. ? No activity was observed without UV-A light irradiation. ? During strand scission event radical species are produced. ? This complex is able to cleave DNA with a rate constant of 0.17min?1 which represents a half-life of only 4min.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Yue-Ling Bai, Feifei Xing, Shourong Zhu, Jun Tao A heterometallic triple-chain complex [CuTb2(mal)4(H2O)6]·2H2O (CuTb2, H2mal=d-malic acid) and its isomorphous CuY2 and ZnTb2 have been prepared and characterized, whose magnetic properties are studied by comparison with its analogues. The results indicate that the Cu?Tb interactions in CuTb2 are antiferromagnetic.
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A heterometallic triple-chain complex [CuTb2(mal)4(H2O)6]·2H2O (CuTb2, H2mal=D-malic acid) and its isomorphous CuY2 and ZnTb2 have been prepared and characterized, whose magnetic properties are studied by comparison with its analogues. The results indicate that the Cu?Tb interactions in CuTb2 are antiferromagnetic.? One-Dimensional heterometallic triple-chain complexes with both transition metal and lanthanide ions are very few and novel. ? The substitution method by diamagnetic ions is very effective in investigating the nature of Cu2+···Tb3+ interactions. ? Antiferromagnetic couplings exist between Cu2+ and Tb3+ ions in CuTb2 complex.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Hai-Yan Chen, Dong-Rong Xiao, Juan Yang, Shi-Wei Yan, Jiang-Hong He, Xin Wang, Zhong-Li Ye, En-Bo Wang Hydrothermal reaction of zinc salt with 1,2,4,5-benzenetetracarboxylic acid (H4btec) and 2,4,5-tri(4-pyridyl)-imidazole (Htpim) in the presence of NaOH affords a new entangled metal–organic polymer [Zn2(btec)(Htpim)2]·2H2O (1). Compound 1 displays a new (2D?3D) polythreaded network that is obtained for the first time from the self-assembly from 2D bilayer frameworks with dangling lateral arms, in which each large rectangular cavity of one bilayer is threaded by two dangling lateral arms of two adjacent bilayers coming from two opposite directions. The photoluminescence of 1 is also discussed.
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A new (2D?3D) polythreaded network, that is obtained for the first time from the self-assembly from 2D bilayer frameworks with dangling lateral arms, is reported, which also defines a trinodal (3,4,6)-connected 3D self-threading network if H-bonds are taken into account.? Compound 1 represents the first (2D?3D) polythreaded array assembled by infinite sidearm-containing 2D bilayer frameworks. ? Compound 1 also defines a trinodal (3,4,6)-connected 3D self-threading network if H-bonds are taken into account. ? Compound 1 displays good fluorescent property.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Daniela Cioloboc, Adrian-Raul Tom?a, Grigore Damian, Radu Silaghi-Dumitrescu Chemical reduction of an iron(III) substituted Dawson 5-molybdo-12-tungsto-2-phosphate ?2-K7[Fe(H2O)P2Mo5W12O61]?17H2O complex, with dithionite in aqueous solution is reported alongside with similar data for the monolacunary Dawson molybdo-tungsto-diphosphates ?2-[P2Mo5W12O61]10?. UV–vis absorption and low-temperature EPR (electron paramagnetic resonance) spectra indicate several distinct species and an unprecedented change of spin state at the ferric center, induced indirectly by reduction of the polyoxometalate framework.
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EPR and UV–vis spectra reveal several redox states accessible in a novel iron-substituted Dawson polyoxometalate, including an unprecedented spin-state change? Reduced forms of iron-containing polyoxometalates are detected by UV–vis and EPR. ? Multiple-step reductions are demonstrated. ? EPR data reveal an unusual spin-state shift at the iron during the reduction of the POM.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Xun Feng, Xun Li Ling, Bin Liu, Zhi-Qiang Shi, Jing-Jing Shang, Li-Ya Wang A novel 3d–4f heterometallic coordination polymer, namely, {[Sm2(PBDA)2·2H2O][Zn2(PBDA)2(Cl)2]}n (1), (H2PBDA=3 -(pyridin-3-yl-oxy) benzene ?1,2-dicarboxylic acid) has been hydrothermally synthesized by using samarium(III) nitrate, H2PBDA acid and zinc chloride as raw materials, and characterized by elemental analysis, FT-IR, TG analysis and single crystal X-ray diffraction. Polymer 1 possesses two-dimensional (2D) network containing the original 1D heterometallic chain composed of [Sm2Zn2(PBDA)2] moieties. Variable temperature magnetic susceptibility studies reveal that 1 displays possible weak antiferromagnetic coupling between the neighboring Sm(III) ions, and the photoluminescent properties of polymer 1 as well as free H2PBDA ligand were also investigated.
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A novel 3d–4f heterometallic coordination polymer, {[Sm2(PBDA)2·2H2O] [Zn2(PBDA)2(Cl)2]}n has been hydrothermally synthesized by using samarium(III) nitrate. Complex 1 possesses two-dimensional (2D) network with the original 1D heterometallic chain composed of [Sm2Zn2(PBDA)2] moieties. Magnetic and the luminescent properties of compound 1 were also investigated.? A novel 3d–4f heterometallic coordination polymer, with 4, 4-connected network has been synthesized. ? To the best of our knowledge, complex 1 is the first (4, 4)-connected coordination framework containing nine-coordinated lanthanide as well as four-coordinated transition metal complex unit, so far. ? It displays possible weak antiferromagnetic coupling between the neighboring Sm(III) ions ? the luminescent properties of compound 1 were also investigated.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Mojtaba Bagherzadeh, Mojtaba Amini, Hadi Parastar, Mehdi Jalali-Heravi, Arkady Ellern, L. Keith Woo A new oxido–peroxido molybdenum(VI) complex [MoO(O2)L(CH3OH)] was synthesized, using salicylidene benzoyl hydrazine as tridentate ONO donor Schiff base ligand (H2L). The complex has been characterized by elemental analysis, IR, 1H NMR, molar conductance data, and finally by X-ray structure analysis. This complex functions as facile olefin epoxidation catalyst with hydrogen peroxide (H2O2) as terminal oxidant and sodium hydrogen carbonate (NaHCO3) as a co-catalyst at room temperature. Catalytic potentiality of complex is also exhibited in oxidation of sulfides. The catalyst show very much efficient reactivity in the oxidation reactions giving high yield, turnover number (TON) and selectivity.
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A new oxo–peroxo molybdenum(VI) complex [MoO(O2)L(CH3OH)] was synthesized and characterized. The complex efficiently catalyzes the selective oxidation of sulfides and olfins to the corresponding sulfoxides and epoxides using UHP and H2O2 respectively as an oxidant.? Molybdenum(VI) oxo-peroxo complex is applied in oxidation of olefins and sulfides. ? Hydrogen peroxide (H2O2) and urea hydrogen peroxide (UHP) as oxidant. ? Excellent yield, high TONs and selectivity has been achieved.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Karina P.M. Frin, Kassio P.S. Zanoni, Neyde Y. Murakami Iha Unusual high photoassisted quantum yields for cis-to-trans (?254 nm=0.27±0.05) isomerization of CNstpy coordinated to fac-[Re(CO)3(phen)(CNstpy)]+ were determined along with trans-to-cis ones (?313 nm=0.58±0.02; ?365 nm=0.61±0.06; ?404 nm=0.42±0.02). Additionally, in contrast to other similar rhenium(I) complexes, the cis photoproduct is quasi non-emissive and comparable to the trans-complex. The cis-to-trans photoisomerization is due to the deactivation from the ILcis-CNstpy excited state in competition to the usual 3MLCTRe?phen luminescence. These efficient cis to trans and trans to cis photoisomerization can be conveniently used in light powered molecular machines.
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The Graphical Abstract summarizes all photoisomerization quantum yields determined for fac-[Re(CO)3(phen)(CNstpy)]+, as well as the trans- and cis-complex structures. It evidences the capacity of changing the majoritarian isomer by changing the incident light energy. These efficient cis to trans and trans to cis photoisomerization can be conveniently used in light powered molecular machines.? Efficient photoresponsive Re(I) compound applicable in molecular machines. ? trans/cis apparent and true photoisomerization quantum yields for fac-[Re(CO)3(phen)(CNstpy)]+. ? Unusual photophysical properties of fac-[Re(CO)3(phen)(cis-CNstpy)]+.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Zhi-Li Fang, Sheng-Run Zheng, Jun Fan, Wei-Guang Zhang The zwitterionic ligand H2Bci [H2Bci=1,3-bis(4-carboxybenzyl)-1H-imidazolium] was formed via in situ reaction. Its Eu(III)-organic framework, {[Eu(Bci)2]Cl}n (1), was obtained under hydrothermal conditions. Complex 1 exhibits a 3-fold interpenetrated diamondoid network with double-bridged connectors. Its solid-state luminescent behavior was investigated at room temperature.
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A 3D Eu(II) coordination polymer that exhibits a 3-fold interpenetrated diamondoid network with double-bridged connectors based on a zwitterionic ligand was formed via in situ reaction.? A zwitterionic ligand is formed by in situ reaction. ? A framework exhibits a diamondoid network with double-bridged connectors. ? The first Eu(II) coordination polymer based on 1,3-bis(4-carboxybenzyl)-1H-imidazolium.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Rashid Ilmi, K. Iftikhar Pyrazine bridged dinuclear lanthanide ?-diketonate complexes of the type [(tfaa)3Ln(?-pyz)Ln(tfaa)3] (tfaa is the anion of 1,1,1-trifluoro-2,4-pentanedione; pyz is pyrazine) were isolated by mixing [Ln(tfaa)3] and pyrazine in 2:1 molar ratio in chloroform. The elemental analysis, high yield and only one sharp resonance for the pyrazine moiety in the NMR spectrum are strong enough to support dinuclear complex formation. The oscillator strength of the hypersensitive 4G5/2, 2G7/2?4I9/2 transition of the neodymium complex is approximately two fold higher than the mononuclear [Nd(tfaa)3H2O]. It confirms the presence of two neodymium ions both of which contribute to the oscillator strength. The red and green photoluminescence of Eu–Eu and Tb–Tb complexes, respectively, were scrutinized in solution and discussed.
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Pyrazine-bridged dinuclear complexes have been synthesized. One NMR resonance for pyrazine protons supports symmetric bridging of pyrazine to two [Ln(tfaa)3] units. The oscillator strenght of 4f-4f transitions of the dinuclear complex is twofold larger than the values for mononuclear complex. Eu and Tb complexes gives red and green luminescence, respectively.? Pyrazine-bridged Ln2 complexes of the type [(tfaa)3Ln]2(?-pyz) are discussed. ? Only one NMR resonance due to pyrazine is observed. ? Red and green photoluminescence are observed from Eu and Tb complexes, respectively. ? The low molecular symmetry around Eu is inferred by stark splitting in the 5D0?7F1. ? 5D0?7F2/5D0?7F1 intensity ratio of [(tfaa)3|Eu(?-pyz)Ln(tfaa)3] is about 10.89.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Gra?yna Bartkowiak, Grzegorz Schroeder The interactions between 2,6-diacetylpyridine bis-4-N-ethylthiosemicarbazone (1) and ten lanthanide triflates have been studied by means of electrospray ionization mass spectrometry. The aim of this work is to gain a better insight into the coordination trends of thiosemicarbazones towards lanthanides. Thiosemicarbazone ligand 1 forms with lanthanides stable complexes, which can be observed in the ESI spectra.
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The lanthanide salts, trifluoromethanesulfonates(triflates) La(CF3SO3)3, and the ligand, 2,6-diacetylpyridine bis-4-N-ethylthiosemicarbazone 1, in acetonitrile were infused into the ESI source and positive mass spectra have been obtained.? Electrospray ionization mass spectra of solutions containing thiosemicarbazone, lanthanide triflate and acetonitrile. ? Thiosemicarbazone-lanthanide complexes detected and their structure analyzed. ? Ligand's affinity to fluoride anions confirmed. ? Thiosemicarbazone/lanthanide triflates complexation mainly through deprotonation of the ligand.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Pei Zhao, Lin Cheng, Guo-Yu Yang A new organic–inorganic hybrid zinc borate [Zn(dab)0.5(dab?)0.5(B4O6(OH)2)]·H2O has been hydrothermally synthesized by using 1,4-diaminobutane (dab) as the linkers and characterized by means of elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction, respectively. This compound crystallizes in the monoclinic space group P21/c, a=9.997(3) Å, b=8.371(3) Å, c=16.321(4) Å, ?=111.7(1)°, V=1268.8(7) Å3, Z=4. The structure contains ZnO2N2 tetrahedra, 1,4-dab and B4O7(OH)2 clusters, which interconnect to form a new three-dimensional framework.
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A new organic–inorganic hybrid zinc borate [Zn(dab)0.5(dab?)0.5(B4O6(OH)2)]·H2O has been made under hydrothermal conditions. In the structure, the B4O7(OH)2 cluster units are linked each other to produce a 1-D helical chain and further linked by the Zn2(dab) bridges to form a 2-D layer, which are further connected by another dab? linkers, resulting in a 3-D open-framework.? A new organic–inorganic hybrid zinc borate [{Zn(dab)0.5(dab?)0.5}{B4O8H2}]·H2O has been hydrothermally made. ? It contains ZnO2N2 tetrahedra, dab and B4O7(OH)2 clusters, which links to form a new 3-D framework. ? It represents the first example of zinc borate expanding from 1-D to 2-D/3-D linked through organic amine molecules.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Agnieszka Pladzyk, ?ukasz Ponikiewski, Yanhua Lan, Annie K. Powell A novel nickel(II) cluster [Ni6(?-O)6{SSi(tBuO)3}6(H2O)6(NH3)4] 1 has been synthesized in reaction of NiCl2?6H2O with tri-tert-butoxysilanethiol and ammonia in water solution. The magnetic measurements show the presence of strong antiferromagnetic interactions between magnetic centers.
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A neutral hexanuclear oxo-bridged nickel(II) cluster 1 has been obtained in the reaction of NiCl26H2O, ammonia and tri-tert-butoxysilanethiol in water. Ni(II) ions in 1 are coordinated by ammonia, water and (tBuO)3SiS -. Magnetic measurements show strong antiferromagnetic interactions between the six Ni(II) ions with a zero total spin ground state.? A neutral hexanuclear oxo-bridged nickel (II) cluster has been synthesized. ? Metal ions coordinated by ammonia, water and (tBuO)3SiS?. ? The cluster exhibits the topology of a face-sharing double cubane. ? Magnetic measurements show strong antiferromagnetic interactions between Ni (II) ions. ? The total spin ground state of the compound is zero.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Jaroslaw Piskorz, Ewa Tykarska, Maria Gdaniec, Tomasz Goslinski, Jadwiga Mielcarek A novel porphyrazine possessing two styryl substituents conjugated with each of four diazepine rings was synthesized and characterized using UV–vis, MS MALDI and various NMR techniques. Solvent effects on the electronic absorption spectra of this porphyrazine were determined in protic and aprotic solvents. The changes observed in the electronic absorption spectra seem to result mainly from solvation as there was no correlation between the coordinating strength of the solvent and the red shift. Also the potential photosensitizing activity of this novel porphyrazine was evaluated by measuring its ability to generate singlet oxygen, which was found to reach the yield (??) of 0.11 in DMF.
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A novel porphyrazine possessing two styryl substituents conjugated with each of four diazepine rings was synthesized, characterized and subjected to photochemical studies. Potential photosensitizing activity of the novel porphyrazine was evaluated by measuring its ability to generate singlet oxygen, which was found to reach the yield of 0.11 in DMF.? New symmetrical styryldiazepinoporphyrazine was synthesized and characterized. ? Porphyrazine was subjected to spectroscopic studies including solvatochromic effects. ? Potential photosensitizing activity of novel porphyrazine was evaluated.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Sergey Shuvaev, Oxana Kotova, Valentina Utochnikova, Andrey Vaschenko, Lada Puntus, Vladimir Baulin, Natalia Kuzmina, Aslan Tzivadze Lanthanide complexes with ortho-phosphorylated phenolate ligands LnL3 (Ln = Eu, Tb, Lu; HL1=2-di(p-tolyl)phosphorylphenol; HL2=2-diphenylphosphoryl-4-ethylphenol) were synthesized for the first time and characterized by elemental analysis, FTIR, 1H, 31P NMR spectroscopy, LDI-TOF mass-spectrometry. The energy gap between the triplet energy level and the corresponding resonance level of a lanthanide ion (5D1 for Eu3+ and 5D4 for Tb3+) is optimal for luminescence sensitization of only terbium ions. Bright green photo- and electroluminescence of terbium complexes was demonstrated.
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The interaction between phosphorylated phenols (HL) and sodium hydroxide leads to formation of sodium phosphorylated phenolate (NaL). Reaction between sodium phosphorylated phenolate and inorganic salts of lanthanides (LnCl3·nH2O) leads to formation of lanthanide complexes LnL3.? Lanthanide complexes of aromatic o-phosphorylated phenols were synthesized. ? Luminescent and volatility properties of lanthanide complexes were investigated. ? Thin film of terbium complex was tested as an active layer of OLED.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Yan-Zhi Qin, Wei Ji, Fei Xiao, Xin Zhang, Su Jing A mixed donor macrocyclic ferrocenophane, 1,13-diselena-5,9-dithia[13]ferrocenophane (L), was synthesized. Reaction of L with [M(NCMe)4](PF6)2 (M=Pd, Pt) led to complexes [ML](PF6)2 (M=Pd, Pt). The structures of two complexes have been determined by X-ray crystallography. Cyclic voltammetry shows that, in [ML](PF6)2 (M=Pd, Pt), the half-wave potential of the 1,1?-ferrocenediyl group shifts to much more positive potentials due to the strong through-space interaction between the two metals (Fe…M) and sulfur atoms.
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A mixed donor macrocyclic ferrocenophane 1,13-diselena-5,9-dithia[13]ferrocenophane (L) and its complexes [ML](PF6)2 (M=Pd, Pt) have been synthesized. The structures of two complexes were determined. Cyclic voltammetry shows that the oxidation of the ferrocenyl group shifts much more positively after complexation.? Macrocyclic ferrocenophane 1,13-diselena-5,9-dithia[13]-ferrocenophane was prepared. ? The solid state structures of Pd(II), Pt(II) complexes adopt the c,t,c configuration. ? Sulfur atoms induces more positive shift of ferrocene oxidation after complexation.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Gregorio Guisado-Barrios, Yiteng Zhang, Andrew M. Harkins, David T. Richens Treatment of [(TPA)FeII(CH3CN)2]2+ (TPA=tris(2-pyridylmethyl)amine) with excess (?2Eq) of 3-chloroperoxybenzoic acid (mCPBA) in semi-frozen acetonitrile in liquid N2 vapour generates a rhombic EPR signal assigned to the S=½ low spin acylperoxoiron(III) species [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+5; the elusive precursor on the pathway to [(TPA)FeIII(5-chlorosalicylate)]+4 via putative [(TPA)FeV(O)(O2CC6H4-3Cl)]2+. Formation of cyclohexene epoxide in the presence of added cyclohexene at low temperatures (<?40°C) suggests that intermolecular alkene epoxidation competes successfully with the intramolecular reactions involving 5 to generate 4.
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Treatment of [(TPA)Fe(CH3CN)2]2+1 with excess (?2Eq) of 3-chloroperoxybenzoic acid (mCPBA) in semi-frozen acetonitrile generates an S=½ EPR signal assigned to the low spin acylperoxo iron(III) species; [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+5; the elusive precursor to putative ‘(TPA)FeV(O)’ on the pathway to [(TPA)FeIII(5-chlorosalicylate)]+. Solutions of 5 are also active in promoting cyclohexene epoxidation.? Mixing [(TPA)FeII(CH3CN)2]2+ with ?2eq mCPBA in semi-frozen acetonitrile forms [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+5. ? Detection (by EPR) of 5 for the first time is as a result of mixing the reagents in the semi-frozen acetonitrile medium. ? 5 is the direct precursor of putative ‘(TPA)FeV(O)2+’ on the pathway to [(TPA)FeIII(5-Cl-salicylate)]+, the final product. ? Generation of cyclohexene epoxide shows that intermolecular alkene epoxidation competes with intramolecular CH O-insertion. ? The findings cannot rule out the possibility that acylperoxoiron(III) complexes can themselves promote alkene epoxidation.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Chuanqi Zhang, Chao Chen, Song Liu, Ning Zhang Two coordination polymers, {[Zn(Hpdcd)(bbi)](DMSO)(2H2O)]}n (1) and {[Ni(Hpdcd)(bbi)·H2O]2H2O}n (2) (H3pdcd=1-(4-carboxyphenyl)-2,5-dimethyl, 1H-pyrrole-3,4-dicarboxylic acid, bbi=1,1?-(1,4-butanediyl)bis(imidazole)), have been solvothermally synthesized. 1 shows a 1D isolated tube with a 1D?2D interdigital structure, while 2 exhibits a 2D deeply corrugated layer with a novel (2D?3D) interdigitated architecture.
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The metal ion is first connected by bbi ligand to form metallocycle or meso-helical chain as the subunits, which were further bridged by the partly deprotonated Hpdcd2? ligands to generate a 1D isolated tube and 2D highly undulating layer, respectively.? 1D isolated tube and 2D highly undulating layer were prepared by bbi and H3pdcd. ? Compounds 1 and 2 show a 1D?2D and 2D?3D interdigital structure, respectively. ? The luminescent property of 1 has been investigated.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Carlos García, Claudia García, Carlos Paucar The synthesis of hydroxyapatite nanoparticles is reported using a hydrothermal microemulsion technique with calcium nitrate tetrahydrate and diammonium hydrogen phosphate as precursors is reported. The advantage of this proposed technique over other previously reported techniques is that particles with controlled size and morphology can be obtained with a new microemulsion with cetyltrimethylammonium bromide (CTAB)/toluene/n-butanol/water as a nanoreactor. X-ray diffraction (XRD) analysis showed that the hydrothermal microemulsion produced powders with phase-pure hexagonal hydroxyapatite. Transmission electron microscopy (TEM) showed that nanoparticles with both defined and undefined shapes can be obtained. Hydroxyapatite nanoparticles with a typical hexagonal prism-like morphology were obtained when microemulsion parameters such as the water to surfactant molar ratio (W0) and the cosurfactant to surfactant molar ratio (P0) were adjusted to defined values. The effects of changes in microemulsion parameters (W0 and P0) on sizes calculated using both transmission electron microscopy (TEM) and dynamic light scattering (DLS) were also investigated; the observed trends are discussed in terms of the interaction between amphiphilic molecules and hydroxyapatite precursor ions at the water–oil (W/O) interfaces.
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The synthesis of hydroxyapatite nanoparticles is reported using a hydrothermal microemulsion technique. Particles with controlled size and morphology were obtained. X-ray diffraction (XRD) analysis showed that the hydrothermal microemulsion produced powders with phase-pure hexagonal hydroxyapatite. Transmission electron microscopy (TEM) showed that nanoparticles with both defined and undefined shapes can be obtained.? Hydroxyapatite nanoparticles were synthesised using a hydrothermal microemulsion technique. ? Cetyltrimethylammonium bromide (CTAB)/toluene/n-butanol/water as nanoreactor. ? Water to surfactant molar ratio (W0) and cosurfactant to surfactant molar ratio (P0). ? Interaction between amphiphilic molecules and hydroxyapatite precursor ions at the water–oil (W/O) interfaces.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Dong Zhao, Lei Wang, Yuan Li, Linfei Zhang, Yunhai Lv, Shengliang Zhong Uniform europium-based infinite coordination polymer (ICP) submicrospheres have been prepared via a facile and fast microwave heating method in 5min, with pyridine-2, 5-dicarboxylic acid and europium nitrate as reagents and N, N-dimethylformamide (DMF) as solvent. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR). Thermogravimetric (TG) and derivative thermogravimetric analysis (DTG) were also carried out. XRD results reveal that the product is amorphous. SEM and TEM results show that the submicrospheres are with diameters of 200–400nm. Furthermore, the surface of the microspheres is smooth and the submicrospheres are solid. Strong red emission centering at 618nm was observed in the europium-based ICP microspheres on excitation with 394nm UV light. This method may be employed to the preparation of other coordination polymers micro/nanostructures.
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Uniform europium-based infinite coordination polymer submicrospheres have been prepared from pyridine-2, 5-dicarboxylic acid and europium nitrate via a facile and fast microwave heating method in 5min,? Infinite coordination polymer spheres have been prepared via a facile and fast microwave method. ? The spheres are uniform and are with diameters of 200–400nm. ? Strong red emission was realized in the submicrospheres.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Yue Wang, Fang-Hua Zhao, Ai-Hua Shi, Yun-Xia Che, Ji-Min Zheng Two Co(II) complexes, [Co(bimb)(L1)2] (1) and [Co(bix)(L2)] (2) (bimb=1,4-bis(imidazol-1–yl)-butane, bix=1,4-bis(imidazol-1-yl-methylene)-benzene, HL1=3,5-dinitro-benzoic acid, H2L2=o-phthalic acid), have been successfully prepared based on achiral flexible bis(imidazole) ligands via spontaneous resolution. Complexes 1 and 2 crystallize in the asymmetrical monoclinic with P21 and Cc space groups, respectively. Interestingly, magnetic studies reveal that complex 1 demonstrates dominant ferromagnetic behavior and complex 2 displays spin-canting behavior. More interestingly, both complexes 1 and 2 exhibit ferroelectric features representing electric hysteresis loops with the saturation polarization (Ps) of ca. 0.085?Ccm?2 and 0.141?Ccm?2.
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This work reported two complexes based on flexible bis(imidazole) ligands with aromatic carboxylate ligands. And the focus on their magnetic and ferroelectric properties has been investigated in detail.? Two complexes based on flexible bis(imidazole) ligands have been presented. ? Both ferromagnetic and ferroelectric behaviors were observed for complex 1. ? Spin-canting and ferroelectric behaviors were observed for complex 2.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Xin Zhang, Jian-Kai Cheng, Ming-Jian Zhang, Yuan-Gen Yao A novel luminescent Cu(I) compound, [Cu(HtrzS)]n (1 HtrzSH=1H-1,2,4-triazole-3-thiol), was hydrothermally synthesized, which features a two-dimensional (2D) inorganic–organic hybrid framework containing a inorganic [CuS]n layer. Further, this 2D framework is connected by the intermolecular hydrogen bonds into a three-dimensional (3D) supramolecular framework. Optical diffuse reflectance study reveals an optical band gap of 3.44eV, making it a wide band gap semiconductor. Moreover, this compound exhibits strong photoluminescence at room temperature. The densities of states (DOS) calculations reveal that luminescence emission bands of the compound originate from the ligand-to-metal charge transfer.
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Presented here is a new luminescent Cu(I) complex, [Cu(HtrzS)]n (1 HtrzSH =1H-1,2,4-triazole-3-thiol), which features a two-dimensional (2D) inorganic–organic hybrid framework containing a inorganic [CuS]n layer.? A new luminescent Cu(I) was synthesized and characterized. ? The complex features an inorganic [CuS]n layer. ? Optical diffuse reflectance study reveals an optical band gap of 3.44eV.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Chao Wang, Ya-li Wang, Zi-xuan Qin, Yue Ma, Qing-lun Wang, Li-cun Li, Dai-zheng Liao Three new lanthanide-radical complexes containing the same radical ligand were successfully synthesized, which all display radical-Ln(III)-radical (Ln=Pr (1), Gd (2), Ho(3)) tri-spin structures. The magnetic studies revealed that, for complex 2, the interactions between the Gd(III) ion and radical are ferromagnetic, while the interaction between two radicals is antiferromagnetic. In complexes 1 and 3, antiferromagnetic couplings exist between the lanthanide ions and radicals.
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The crystal structures and magnetic properties of three new lanthanide-radical complexes were fully characterized. Complex based on Gd(III) ion have both ferromagnetic and antiferromagnetic interactions in one molecule, and other complexes were roughly estimated through a simplified model.? Three lanthanide-radical complexes were successfully synthesized. ? Both ferromagnetic and antiferromagnetic interactions exist in complex 2. ? Simplified models were carried out to evaluate the coupling in complexes 1 and 3.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Yu-E Cha, Xue Ma, Xia Li, Han-Zhu Shi, Hua-Lu Tan, Yuan Meng Two coordination polymers, [M(Fpht)tib]·H2O (M=Cd 1, Co 2; H2Fpht=3-fluorophthalic acid and tib=1,3,5-tris(1-imidazolyl)benzene) have been synthesized and structurally characterized by single crystal X-ray diffraction. They possess unusual double layer structures constructed from M–Fpht helices and (3, 3) M–tib honeycom layers. The fluorescence of the complexes maybe arise from the intraligand ??–? transition.
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Two coordination polymers, [M(Fpht)tib]•H2O (M=Cd 1, Co 2; H2Fpht=3- fluorophthalic acid and tib=1,3,5-tris(1-imidazolyl)benzene) have been synthesized and structurally characterized. They possess unusual double layer structures constructed from M-Fpht helices and (3, 3) M-tib honeycom layers.? Unusual 2D double layer structure is constructed from Cd(II)/Co(II) ions with 3-fluorophthalic acid (H2Fpht) and 1,3,5-tris(1-imidazolyl)benzene) (tib). ? Each tib ligand connects three M(II) ions and each M(II) ion connects three tib ligands to generate an (3, 3) M–tib honeycom layer. ? M(II) ions are linked together by the Fpht ligands to form M–Fpht right- and left-handed helical chains. ? 3D supramolecular network is formed by C?H…? or ?…? interaction.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Takuma Ohkubo, Koichiro Takao, Taro Tsubomura Photoluminescence properties of palladium(0) complexes bearing monodentate phosphines are described. [Pd(P(o-tol)3)2] (o-tol=ortho-tolyl) emits relatively strong blue luminescence in the solid state. Whereas, [Pd(PCyPh2)3] (Cy=cyclohexyl) and [Pd(PCy3)2] show orange luminescence with a large Stokes-shift. The crystal structure analysis of [Pd(PCyPh2)3] reveals the trigonal planar geometry around the palladium atom.
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Palladium(0) complexes bearing monodentate phosphines emit blue to orange luminescence. [Pd(P(o-tol)3)2] shows blue emission in the solid state. Both of [Pd(PCyPh2)3] and [Pd(PCy3)2] show orange emissions with a large Stokes-shift in the solid state.? Blue to orange luminescence has been observed for palladium(0) complexes bearing monodentate phosphines. ? Blue luminescence was found for [Pd(P(o-tol3)2)]. ? Other two complexes show orange emission with an unusual large Stokes-shift.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Xiu-Ting Wang, Yue-Ling Bai, Feifei Xing, Min Shao, Shourong Zhu Two coordination polymers {[Zn(fum)(btmb)]·3H2O}n (1) and {[Zn(2,3-pzdc)(tttmb)(H2O)2]·H2O}n (2) (H2fum=fumaric acid, btmb=4,4?-bis(1,2,4-triazol-1-ylmethyl)biphenyl, 2,3-H2pzdc=2,3-pyrazinedicarboxylic acid, tttmb=1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene) have been synthesized and structurally characterized. Compound 1 is a two-fold interpenetrating 2D network; significant ?–? interactions in adjacent layers finally result in a 3D supramolecular framework with 14.167×7.831Å channel. Compound 2 is a 1D chain. The guest molecules (fluorescein and phenylfluorone) adsorption behaviors of 1 and luminescent properties of 1 and 2 have been investigated.
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Two coordination polymers {[Zn(fum)(btmb)]·3H2O}n (1) and {[Zn(2,3-pzdc)(tttmb)(H2O)2]·H2O}n (2) (H2fum=fumaric acid, btmb=4,4?-bis(1,2,4-triazol-1-ylmethyl)biphenyl, 2,3-H2pzdc=2,3-pyrazinedicarboxylic acid, tttmb=1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene) have been synthesized and structurally characterized. 1 was a two-fold interpenetrating 2D network and ultimately formed a 3D supramolecular framework with large channel from significant ?–? interactions in adjacent layers, which can respectively adsorb guest molecules of fluorescein and phenylfluorone. The adsorption behaviors were approved by elemental analysis, PXRD and luminescent.? Compound 1 is a two-fold interpenetrating 2D network, which finally results in a 3D supramolecular framework with large channel by significant ?–? interactions in adjacent layers. ? Compound 1 can adsorb guest molecules of fluorescein and phenylfluorone, respectively. ? The adsorption behaviors were approved by elemental analysis, PXRD and luminescent.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Shi-Zhou, Zhi-Guo Kong, Qing-Wei Wang, Chuan-Bi Li A novel metal-organic framework (MOF), namely, [Ag3(tptz)3(Mo5O17)](H3O)(H2O)1.5 (1), where tptz=2,4,6-tri(4-pyridyl)-1,3,5-triazine, has been prepared under hydrothermal condition. Compound 1 is a chiral three-fold interpenetrated 3D MOF, in which the [Mo5O17]4? anions act as templates, encapsulated in the chiral channels of the 3D framework.
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A novel 3D POM-templated three-fold interpenetrating MOF based on the rigid 2,4,6-tri(4-pyridyl)-1,3,5-triazine ligand has been successfully synthesized, where the optical band gap and the photoluminescent property have also been investigated.? We synthesized an exceedingly rare case of interpenetrating networks with polyoxometalates as templates. ? We investigated the conductivity of the compound. ? We studied the photoluminescent property of the compound. ? The compound is chiral. ? The [Mo5O17]4? anion in the compound is rare.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Li-Na Cui, Zhong-Feng Li, Qiong-Hua Jin, Xiu-Lan Xin, Cun-Lin Zhang Two new silver(I) complexes [Ag2(?-dppb)2(CF3SO3)2] (1) and {[Ag2(dppb)3](CF3SO3)2•(4,4?-bipy)•(CH3CN)2}n (2) (dppb=bis(diphenylphosphino)butane, 4,4?-bipy=4,4?-bipyridine) which contain dppb and trifluoromethanesulfonate anions have been synthesized and characterized by IR, X-ray crystallography, 1H NMR, 31P NMR spectroscopy and luminescence. Complex 1 and 4,4?-bipy reacted in the solution CH3CN to get complex 2. In the reaction, the 14-membered ring [Ag2(?-dppb)2] of complex 1 is opened to form the “honeycomb” (6, 3) network structure of complex 2. In 2, each [Ag6(?-dppb) 6] 6+ ring hosts two counterions, one 4,4?-bipy and two acetonitrile guest molecules.
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Induced by nitrogen heterocyclic ligands, [Ag2(dppb)2(CF3SO3)2] (1) was obtained. The 14-membered ring [Ag2(?-dppb)2] of 1 is opened to form (6,3) network structure of {[Ag2(dppb)3](CF3SO3)2•(4,4?-bipy)•(CH3CN)2}n (2). In 2, each [Ag6(?-dppb) 6] 6+ ring hosts CF3SO3?, 4,4’-bipy and acetonitrile molecules. 1–2 were characterized by IR, luminescence, 1H NMR, 31P NMR, and X-ray crystal diffraction.? The (6,3) network structure of 2 is formed by the ring-opening reaction of 1 with 4,4?-bipyridine. ? In 2, each [Ag6(?-dppb) 6] 6+ macrocycle hosts CF3SO3- anions, 4,4?-bipy and acetonitrile molecules. ? The skeletons of silver(I)–dppb complexes are affected by the nitrogen heterocyclic ligands and the solvent. ? 1–2 exhibit strong fluorescence emission peaks at room temperature. ? The 31P NMR spectra of 1or 2 shows that the P atoms coordinated to the center Ag atom have different chemical environment.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Hui Yang, Tie hu Li, Yao Kang, Fei Wang A new three-dimensional (3D) metal-organic framework (MOF) [Cd(tpa)Cl](CH3)4N+ (1; tpa=1, 4-terephthalic acid) with unusual Cd2 (COO)4Cl2 building block has been solvothermally synthesized and structurally characterized by the aid of single crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) Elemental analysis (EA) and Infrared Spectroscopy (IR). The Cd2(COO)4Cl2 building block can be simplified as 4-connected or two 3-connected nods in different ways, correspondingly, the compound 1 exhibits 4-connected dia or 3-connected ths structural topology.
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Presented here is a new 4-connected dia or 3-connected ths cadmium-organic framework with unusual Cd2(COO)4Cl2 building blocks.? A metal-organic framework with unusual Cd2(COO)4Cl2 building blocks. ? A metal-organic framework with dia or ths structural topology. ? Solvothermal synthesis of a photoluminescent compound.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Shaban Y. Shaban, Abd El-Motaleb M. Ramadan, Frank W. Heinemann Two dianionic amine bis(thiolato) ligands are introduced and their reactions with titanium tetra(iso-propoxide) studied; ligand N2H2S2H2 (1) having NH donor groups leads exclusively to dinuclear [{Ti(N2H2S2)(OiPr)}2] (2) along with an oxidation product of the ligand (3) whereas ligand N2Me2S2H2 (4) having an additional N-substituent leads exclusively to a mononuclear [Ti(N2Me2S2)(OiPr)2)] (5) type complex.
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Two dianionic amine bis(thiolato) ligands are introduced and their reactions with titanium tetra(iso-propoxide) studied. Ligand N2H2S2-H2 (1) having NH donor groups leads to dinuclear [{Ti(N2H2S2)(OiPr)}2] (2) along with an oxidation product of the ligand (3) whereas ligand N2Me2S2-H2 (4) having an additional N-substituent leads to a mononuclear [Ti(N2Me2S2)(OiPr)2] (5) type complex. ? Synthesis of new titanium complexes containing mixed NS-ligands. ? Effect of steric bulk on coordination features. ? Oxidation of thiolates to disulfides using titanium (IV).
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Tatiana R. Amarante, Patrícia Neves, Filipe A. Almeida Paz, Martyn Pillinger, Anabela A. Valente, Isabel S. Gonçalves The dinuclear complex [Mo2O6(di-tBu-bipy)2] (1) (di-tBu-bipy=4,4?-di-tert-butyl-2,2?-bipyridine) was obtained as a minor product of the hydrothermal reaction of MoO3 and di-tBu-bipy, and structurally characterized by single-crystal X-ray diffraction. In the molecular structure of 1 two distorted MoO6 octahedra share a common edge to form a dioxo-bridged Mo2O6 unit which is coordinated by di-tBu-bipy ligands. The catalytic performance of 1 for the epoxidation of non-functionalized olefins using tert-butylhydroperoxide as oxidant compares favorably with that reported for other oxomolybdenum(VI) complexes bearing the same organic ligand. The catalyst exhibits regioselectivity toward internal olefin epoxidation over external olefin epoxidation.
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A rare example of a dinuclear molybdenum complex exhibiting the {Mo2O6}0 core has been isolated from the hydrothermal reaction of MoO3 and 4,4?-di-tert-butyl-2,2?-bipyridine, and structurally characterized by single crystal X-ray diffraction. The complex is a particularly active and regioselective catalyst for the epoxidation of non-functionalized olefins using tert-butylhydroperoxide as oxidant.? The structure of a rare example of a dinuclear molybdenum complex exhibiting the {Mo2O6}0 core is described. ? Crystals of the complex were obtained after the hydrothermal reaction of MoO3 and 4,4?-di-tert-butyl-2,2?-bipyridine. ? The dioxo-bridged complex possesses catalytic activity for the epoxidation of non-functionalized olefins. ? The catalytic reaction is regioselective toward the epoxidation of internal double bonds.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Qian Li, Dongdong Sun, Yanhui Zhou, Du Liu, Qianling Zhang, Jie Liu A novel Ru(II)–selenium complex [Ru(phen)2L](ClO4)2 (phen=1,10-phenanthroline, L=1,10-phenanthrolineselenazole) has been synthesized and structurally characterized by elemental analysis, ESI-MS and 1H NMR spectra, and the interaction between human telomeric G-quadruplex DNA (HTG21) and the new compound has been studied by emission spectra, visual detection assay, circular dichroism (CD) spectroscopy and fluorescence resonance energy transfer (FRET) melting assay. The results show that the complex has interaction with human telomeric G-quadruplex DNA which is visually detected, meanwhile it induces the guanine-rich single-strand oligomer d[G3(T2AG3)3] to form antiparallel G-quadruplex and has a moderate ability to stabilize G-quadruplex structures (?Tm=11.2°C). Furthermore, polymerase chain reaction-stop assay, telomerase repeat amplification protocol, and MTT assay demonstrate that the Ru-complex can exhibit well inhibitory activity for telomerase and cancer cells. The results suggest that Ru-complex may be a potential telomerase inhibitor for cancer chemotherapy.
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The scheme is the structure of the Ru-complex and its activity in PCR-stop assay.? This is the first report demonstrating that a novel ruthenium complex with selenium binding to G-quadruplexes. ? The Ru-complex induces the oligomer d[G3(T2AG3)3] to form and stabilize antiparallel G-quadruplex. ? TRAP assay demonstrate that the novel Ru-complex can exhibit well inhibitory activity for telomerase and cancer cells.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Wei-Xu Feng, Ya-Ni Hui, Guo-Xiang Shi, Dan Zou, Xing-Qiang Lü, Ji-Rong Song, Dai-Di Fan, Wai-Kwok Wong, Richard A. Jones With the Zn-Schiff-base [ZnL(CH3CN)] from the Salen-type Schiff-base ligand H2L (H2L=N,N?-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) with the flexible linker as the precursor, a series of hetero-trinuclear Zn2Ln complexes [Zn2Ln(L)2(Cl)3] (Ln=Nd, 1; Ln=Yb, 2; Ln=Er, 3; Ln=Gd, 4) are obtained by the further reaction with LnCl3·6H2O, respectively. The results of their photophysical studies show that the strong and characteristic NIR luminescence with emissive lifetimes in the microsecond range, has been sensitized from the excited state (both 1LC and 3LC) of the ligand due to the effective intramolecular energy transfer.
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Synthesis, structure and near-infrared (NIR) luminescence of series of Zn2Ln (Ln=Nd, Yb or Er) complexes based on the Salen-type Schiff-base ligand with the flexible linker are reported.? Trinuclear Zn2Ln complexes based on the Salen-type Schiff-base ligand with the flexible linker. ? Effective sensitization and efficient energy transfer. ? Enhanced near-infrared luminescent properties.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Lili Zhang, Hengchao Zhang, Weisong Zhang, Hailiang Hu, Yang Liu, Zhenhui Kang A new hybrid compound [Cu(en)2]4[Na2VV14VIV2O42(VIVO4)]·2H2O (1) (en = ethylenediamine) has been hydrothermally synthesized. Single-crystal structural analysis indicates that compound 1 contains a novel bisodium-substituted [Na2V16O42(VO4)]8? cluster (abbreviated as Na2V16) with an encapsulated [VO4]4? core. The Na2V16 cluster exhibits a eight-connected model by providing eight terminal O atoms to link eight [Cu(en)2]2+ units, generating a three-dimensional (3D) network with 412·63 topology. Furthermore, the electrochemical property of 1 has been studied.
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A new 3D framework with an 6-connected topology based on a novel bisodium-substituted [Na2V16O42(VO4)]8? cluster encapsulated with [VO4]4? core has been successfully isolated and structurally characterized.? Novel bisubstituted [Na2V16O42(VO4)]8? cluster encapsulated with [VO4]4? core. ? The important role of big and highly charged [SO4]4? and [PO4]3? anions. ? The uncommon CV behavior of the title compound.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Kaushik Ghosh, Nidhi Tyagi, Pramod Kumar, Sweety Rathi, Udai P. Singh A new dinucleating ligand N,N?-diphenyl-N,N?-di(pyridin-2-yl)oxalohydrazide (GampH2) has been synthesized and GampH2 gave rise to complex [Fe2(Gamp)(DMF)2Cl4], 1 with FeCl3 salt and 1 was isolated as shiny blue crystalline solid. The molecular structure of complex 1 was characterized by X-ray crystallography. In this dinuclear complex, Fe–Fe separation was found to be 5.49Å and variable temperature magnetic moment was examined. Electrochemical investigation afforded a quasireversible redox couple with E1/2 value of 0.144V vs Ag/AgCl. Complex 1 was efficient in DNA cleavage activity and enhancement of DNA cleavage was observed in the presence of 2-mercaptoethanol and hydrogen peroxide. Investigation of mechanism indicated possible involvement of hydroxyl radical in nuclease activity.
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A novel dinuclear iron(III) complex was synthesized and its structure was determined by X-ray crystallography. The complex itself exhibited DNA cleavage at high concentration; however, the efficiency was increased with the increase in incubation time and enhancement of nuclease activity was observed in presence of H2O2 and BME.? A dinuclear iron complex was synthesized and characterized by spectroscopic studies. ? Molecular structure of the complex was determined by X-ray crystallography. ? Nuclease activity was investigated.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Damir A. Safin, Maria G. Babashkina, Michael Bolte, Yann Garcia Reactions of the sodium salts of PhC(S)NHP(Y)(OiPr)2 (Y=S, HLI; O, HLII) with PPh4Br in 96% aqueous EtOH leads to the corresponding compounds PPh4LI,II. The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopies; their compositions were examined by microanalysis. Recrystallization of PPh4LI,II from EtOH/H2O solution (1:1, v/v) leads to the formation of HLII and PhC(O)NHP(O)(OiPr)2 (HLIII), respectively. The crystal structures of HLII,III are reported and compared with the previously reported polymorphs.
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Reactions of the sodium salts of PhC(S)NHP(Y)(OiPr)2 (Y=S, HLI; O, HLII) with PPh4Br give the corresponding compounds PPh4LI,II. Recrystallization of PPh4LI,II from EtOH/H2O solution leads to the formation of HLII and PhC(O)NHP(O)(OiPr)2 (HLIII), respectively. The crystal structures of HLII,III are reported and compared with the previously reported polymorphs.? Tetraphenylphosphonium salts of PhC(S)NHP(Y)(OiPr)2 (Y=S, O) are reported. ? The compounds were examined by IR, 1H and 31P{1H} NMR spectroscopy. ? New crystal polymorphs of PhC(X)NHP(O)(OiPr)2 (X=S, O) were obtained.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Li-Zhi Zhang, Guo-Yong An, Min Yang, Ming-Xue Li, Xian-Feng Zhu Main group metal complex [Bi(HL)(NO3)3] (1), where HL=2-acetylpyrazine N(4)-pyridylthiosemicarbazone, has been synthesized and characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction studies. The interesting monomeric 8-coordinate bismuth(III) complex 1 is depicted with one electron pair (6s2) of the bismuth(III) atom, one N2S tridentate neutral thiosemicarbazone, two monodentate and one bidentate nitrate ions, respectively. In vitro biological studies have indicated that the bismuth complex 1 has shown effective antibacterial and anticancer activities especially with MIC=15.6?g/mL against Gram positive bacteria Bacillus cereus and IC50=1.6 ?M against K562 leukemia cell lines, respectively, comparable to positive control.
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Main group metal complex [Bi(HL)(NO3)3] (1), where HL=2-acetylpyrazine N(4)-pyridylthiosemicarbazone, has been synthesized and structurally characterized. Formation of 8-coordinated structure of the bismuth(III) atom is unusual and interesting. Biological studies have indicated that the bismuth(III) complex shown effective antibacterial and anticancer activities, especially with MIC=15.6?g/mL against Gram positive bacteria Bacillus cereus and IC50=1.6?M against K562 leukemia cell lines, respectively, comparable to positive control.? Bismuth(III) complex [Bi(HL)(NO3)3] (1) has been synthesized and characterized. ? Formation of 8-coordinated structure of the bismuth(III) atom is unusual. ? The bismuth complex 1 shown effective biological activities. ? These results are encouraging its further screening and evaluation of mechanism.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 David Specklin, Clarisse Tourbillon, Vitor Rosa, Mohamedally Kurmoo, Richard Welter A new MnIV dinuclear complex [MnIV2(?-O)2(L?)4].2CH3OH (HL?=(E)-N?-(1-(thiophen-2-yl)ethylidene)benzohydrazide) was obtained from MnIII(acetate)3.2H2O by an unusual MnIII disproportionation reaction. This compound exhibits a strong antiferromagnetic coupling with a J value of ?149(5) cm?1. Moreover, a new MnIII mononuclear complex bearing L? named [MnIII(acac)(L?)2] (acac = acetylacetonate) was obtained from [MnIII(acac)3] and is described as a part of a systematic research work around manganese complexes of magnetic interest.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Wei Guo, Xu-Dong Chen, Miao Du, Albert Escuer Solvothermal reaction of Ni(OAc)2 with the new ligand 1,2-di(pyridin-2-yl)ethanone (HL) in the presence of NH4SCN in DMF/CH3OH solution affords a novel trinuclear Ni2+ complex [Ni3(L)2(OAc)2(SCN)2(DMF)2](DMF)1.5(H2O) (1). Crystal structure determination of 1 reveals a non-collinear Ni3-pattern bridged by the ?2-Oenolate atoms of L? and ?3-acetate anions, which has rarely been found for trinuclear Ni2+ systems. Moderate ferromagnetic exchange was observed between the Ni2+ centers.
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This work presents the synthesis, crystal structure, and magnetism of a novel trinuclear Ni2+ complex with 1,2-di(pyridin-2-yl)ethanone (HL), in which the non-collinear Ni3-core is bridged by both ?2-Oenolate of L? and ?3-acetate anions, exhibiting overall ferromagnetic interactions between Ni2+ centers.? A non-collinear [Ni2+]3 complex linked by ?2-Oenolate and ?3-acetate has been reported. ? 1,2-Di(pyridin-2-yl)ethanone tends to the enolate form in the complex. ? All interactions between Ni2+centers are ferromagnetic.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Yaqiu Tao, Edwin C. Constable, Catherine E. Housecroft, Markus Neuburger The syntheses and characterizations of 4?-phenylthio-2,2?:6?,2?-terpyridine (4?-PhStpy) and [Fe(4?-PhStpy)2][PF6]2 are reported. In the solid state, centrosymmetric pairs of [Fe(4?-PhStpy)2]2+ cations in [Fe(4?-PhStpy)2][PF6]2·2MeCN associate through face-to-face ?-stacking of pyridine rings, and twisting of the PhS substituents enables the cations to embrace one another, capturing four MeCN solvate molecules within the {Fe(4?-PhStpy)2}2-motif.
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Assembly of centrosymmetric pairs of [Fe(4?-PhStpy)2]2+ cations (4?-PhStpy = 4?-phenylthio-2,2?:6?,2?-terpyridine) results in a {Fe(4?-PhStpy)2}2-host that captures four MeCN molecules in [Fe(4?-PhStpy)2][PF6]2·2MeCN.? 4?-Phenylthio-2,2?:6?,2?-terpyridine (4?-PhStpy) ligand. ? Crystal structures of 4?-PhStpy and [Fe(4?-PhStpy)2][PF6]2. ? Centrosymmetric embrace of [Fe(4?-PhStpy)2]2+ cations. ? Host–guest interactions.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Shunsheng Zhao, Xiangrong Liu, Weixu Feng, Xingqiang Lü, Wai-Yeung Wong, Wai-Kwok Wong With ZnL1 or ZnL2 from the simple Salen-type Schiff-base ligand H2L1 (H2L1?N,N?-bis(3-methoxysalicylidene)-ethylene-1,2-diamine) or the carbazole-modified Salen-type Schiff-base ligand H2L2 (H2L2?N,N?-bis(3-methoxy-5-{2-[4-(N-carbazyl)-phenyl]-ethynyl}-ethylene-1,2-diamine) as the precursor, two series of four bimetallic ZnLn complexes (Ln=Nd(1 or 3), Ln=Gd (2 or 4) are obtained, respectively. The photophysical properties results showed that the sensitization from the excited state (1LC and 3LC) of the ligand H2L1 or H2L2 and the effective energy transfer of Zn2+-Schiff-base (ZnL1 or ZnL2) to the Nd3+ ion for the NIR luminescence were realized, respectively. Especially through the cabarzole modification, the improved NIR luminescence of the ZnNd complex 3 was observed due to the realization of the energy level's match of the excited state of the chromophore to the Nd3+ ion's exciting state.
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In the Zn–Nd Schiff-base complexes from H2L1 or the carbazole-modified H2L2, through the carbazole modification, the improved NIR luminescence of the ZnNd complex 3 was observed, due to the avoiding of the luminescent quenching effect arising from OH-, CH- or NH-oscillators of the solvates around the Nd3+ ion in combination with the realization of the energy level's match of the excited state of the chromophore to the Nd3+ ion's exciting state.? Carbazole-modified Salen-type Schiff-base ligand. ? Effective sensitization and efficient energy transfer. ? Enhancement of near-infrared luminescence of the Zn–Nd binuclear Schiff-base complexes.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Mohamed Ghazzali, Mohammed H. Jaafar, Khalid Al-Farhan, Sebastiaan Akerboom, Jan Reedijk A new alternating chain compound consisting of gold(I) and silver(I) bridged by cyanides is reported. The Ag(I) ion is functionalized by 2 triphenyl phosphane ligands, resulting in the formula [Au(CN)2(PPh3)2Ag]n. The compound has been prepared by room temperature reaction of triphenyl phosphane with the cyanide salts of silver(I) and gold(I). The product has been characterized and its single crystal X-ray structure was determined. In the molecular structure of the complex, the Au(I) centers exhibit the expected linear, two-coordinate geometry with C-bound cyanides, whereas the Ag(I) centers adopt a tetrahedral geometry in a AgN2P2 chromophore. The shortest hetero intermetallic separation distance is 4.94(7) Å. No aurophilic interactions are observed, but only the non-conventional CH…Au hydrogen interactions are present. Upon excitation at 325nm, a quite intense luminescence at 475nm, assigned on the basis of DFT calculations to MMLCT, is observed, which amounts to ca. 10% of the luminescence intensity of the best known luminescent compounds.
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The AgI-AuI compound of formula [Au(C?N)2(PPh3)2Ag]n for one-dimensional coordination polymer exhibits luminescence around 475 nm, by excitation at 325 nm.? New AgI–AuI dinuclear cyanido-bridged chain compound has been prepared. ? One-dimensional zig-zag like coordination polymer along the crystallographic c-axis. ? Exciting the title compound at 325nm results in luminescence around 475nm in a high yield.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Tianliang Ma, Jian Zhang, Xuemin Jing, Quan Feng, Bing Zheng, Yang Yu, Qisheng Huo, Yunling Liu Three novel 3D lanthanide organic frameworks [Ln2(H2O)3(HMImDC)2(OX)]·4H2O (Ln=Sm(1), Eu(2) and Gd(3), H3MImDC=2-methyl-4,5-imidazoledicarboxylic acid, OX=oxalic acid) have been solvothermally synthesized and structurally characterized by elemental analyses, Infrared spectra (IR), thermogravimetric analyses (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions. Compounds 1–3 are isostructural and exhibit novel 3D architectures with open channels viewed along the a axis, which constructed from [Ln(HMImDC)(OX)] layers and Ln2(HMImDC)2 dimers. The framework of 1–3 can be rationalized as a (3, 5)-connected net with a unique (4.5.7)2(5.6.7)(52.63.7.83.10) topology. The luminescence and magnetic properties are also investigated.
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Structural views of the three three-dimensional coordination polymers [Ln2(H2O)3(HMImDC)2(OX)]·4H2O (Ln=Sm(1), Eu(2) and Gd(3)). In the structure, the lanthanide ions coordinate with 2-methyl-4,5-imidazoledicarboxylate and oxalic acid mixed ligands to give a 2D layer, which is further connected by the Ln2(HMImDC)2 dimers to construct 3D frameworks with (3,5)-connected network.? Lanthanide organic frameworks based on 2-methyl-4,5-imidazoledicarboxylate and oxalic acid mixed ligands. ? Compounds 1–3 have (3, 5)-connected networks. ? Compound 2 exhibits strong red luminescence emission. ? Compound 3 shows weak antiferromagnetic interactions.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Zhi-Shu Wang, Zhi-Ming Zhang, Xin-Bao Han, Huan Zhang, En-Bo Wang Two new compounds constructed from mixture-valence {Fe6}-cluster-containing sandwich-type tungstoferrates functionalized by N-donor ligands, (H2enMe)5{FeIII2FeII2(HenMe)2[B-?-FeW9O34]2}?12H2O (1) and (H2enMe)3FeII(enMe)2H2{FeIII2FeII2 (HenMe)2[B-?-FeIIIW9O34]2}?13H2O (2) (enMe=1,2-diaminopropane) have been synthesized under hydrothermal conditions. Compound 1 is an isolated {Fe6}-cluster-containing sandwich-type tungstoferrate functionalized by two enMe ligands. Compound 2 exhibits a 1-D chain-like structure composed of the sandwich-type polyoxoanions linked by iron linkers via the bridging oxygen atoms, representing the first extended structure based on tungstoferrates. Also, the sandwich-type polyoxoanions coordinating with the transition-metal (TM) linkers with the bridging oxygen atoms is rarely observed in the polyoxometalate (POM) chemistry.
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A mixture-valence {Fe6}-cluster-containing sandwich-type tungstoferrate functionalized by two N-donor ligands has been synthesized under hydrothermal method, and the sandwich tungstoferrates are further linked by iron linkers via the bridging oxygen atoms into a 1-D chain-like structure.? Compounds 1 and 2 are both based on the mixture-valence {Fe6}-cluster-containing sandwich-type tungstoferrates. ? The sandwich structures in these two compounds are both functionalized by two N-donor ligands. ? Compound 2 represents the first extended structure based on tungstoferrates.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Yan-Qing Wen, Yu Ma, Yan-Qin Wang, Xiu-Mei Zhang, En-Qing Gao A new one-dimensional Co(II) coordination polymer, Co(L)(N3)2 (L = pyridinio-N-acetate), has been synthesized by a diffusion method and characterized by single crystal X-ray diffraction. In the compound, Co(II) ions are linked by mixed triple bridges (two end-on azides and a syn–syn carboxylate), which transmit ferromagnetic coupling with J=13.96cm?1. The compound exhibits field-induced metamagnetic behaviors below TN=2.3K with Hc=100Oe, due to weak antiferromagnetic interactions between chains.
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The mixed bis(azido)(carboxylate) triple bridges in the new cobalt(II) chain compound derived from a zwitterionic carboxylate ligand induce ferromagnetic coupling and the compound exhibits metamagnetic behaviors.? Bis(azido)(carboxylato)-bridged magnetic systems from zwitterionic ligands. ? The mixed bridges mediate ferromagnetic exchange between Co(II) ions. ? Metamagnetism due to competitive intrachain and interchain interactions.
Publication year: 2012 Source:Inorganic Chemistry Communications, Volume 20 Jingjing Zhao, Linke Li, Changhong Wang, Wenju Li, Ruina Wang, Xiaofang Zheng, Hongwei Hou Reaction of 4-amino-3-(4-pyridyl)-5-mercapto-1,2,4-triazole (a-Hptt) with PbCl2 hydrothermally has yielded complex [PbCl(ptt)]n (1) at pH 5. And the ligand a-Hptt can be deaminated and transformed into Hptt under hydrothermal condition (pH 5). The structure of 1 has been fully characterized by single crystal X-ray diffraction, elemental analysis, IR, as well as luminescent property. Structural analysis reveals that complex 1 is constructed from 2D two-component layers, which alternately arrange in the ?ABAB? pattern, and then further pillared by Hptt ligands into an interesting 3D “pillared-layer” architecture. Complex 1 also shows strong luminescence emission in solid state at room temperature and may be suitable as a candidate for potentially photoactive material.
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Unusual 3D pillared-layer Pb(II) complex with a (4,8)-connected topology of (32·48·512·62·74)(32·45·53) has been prepared by 4-amino-3-(4-pyridyl)-5-mercapto ?1,2,4-triazole (a-Hptt) under hydrothermal condition. Structural analysis of 1 reveals that a-Hptt can be deaminated and transformed into Hptt at pH 5. 1 also shows strong luminescence emission in solid state at room temperature.? Unusual 3D pillared-layer Pb(II) complex 1 has been obtained by a-Hptt under hydrothermal condition. ? Structural analysis of 1 shows that a-Hptt can be deaminated and transformed into Hptt at pH 5. ? This work provides a potential photoactive material with strong luminescence emission in solid state.
Posted on 27 May 2012 | 1:05 am
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