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Inorganic Chemistry

Jian Wang, Yuan-Yuan Zhao, Po-Heng Lee, Stephan Irle
Metallofullerenes with two erbium atoms encapsulated in IPR C82 cage isomers Cs-6 (I), C2v-9 (II), and C3v-8 (III) were investigated using density functional theory. The calculations suggest that erbium atoms assume a trivalent state with Er (4f(11)) valence electronic configuration in Er2@C82 and Er2C2@C82, where two electrons (6s(2)) per Er atom are transferred to the cage carrying four negative charges (C82(4-)), while the third electron is promoted from the 4f to the 5d shell, becoming involved in covalent bonding to near atoms...
May 24, 2017: Inorganic Chemistry
Hadil Shalan, Alexander Colbert, Thanh Truc Nguyen, Mallory Kato, Lionel Cheruzel
Ru(II)-diimine complexes covalently attached near the heme active site of P450 BM3 enzymes have been used to rapidly inject electrons and drive selective C-H functionalization upon visible light irradiation. Herein, we have generated a series of hybrid P450 BM3 enzymes containing a photosensitizer of general formula [Ru(4,4'-X2bpy)2(PhenA)](2+) where X = Cl, H, tBu, Me OPhe, OMe, or NMe2, bpy = 2,2'-bipyridine, and PhenA = 5-acetamido-1,10-phenanthroline. We then probed the effect of electron-withdrawing and -donating groups at the para position of the 4,4'-X2bpy ligands on the corresponding hybrid enzymes photocatalytic activity...
May 24, 2017: Inorganic Chemistry
Henrik Eickhoff, Lorenzo Toffoletti, Wilhelm Klein, Gabriele Raudaschl-Sieber, Thomas F Fässler
The lithium phosphidosilicates Li10Si2P6 and Li3Si3P7 are obtained by high-temperature reactions of the elements or including binary Li-P precursors. Li10Si2P6 (P21/n, Z = 2, a = 7.2051(4) Å, b = 6.5808(4) Å, c = 11.6405(7) Å, β = 90.580(4)°) features edge-sharing SiP4 double tetrahedra forming [Si2P6](10-) units with a crystal structure isotypic to Na10Si2P6 and Na10Ge2P6. Li3Si3P7 (P21/m, Z = 2, a = 6.3356(4) Å, b = 7.2198(4) Å, c = 10.6176(6) Å, β = 102.941(6)°) crystallizes in a new structure type, wherein SiP4 tetrahedra are linked via common vertices and which are further connected by polyphosphide chains to form unique ∞(2)[Si3P7](3-) double layers...
May 24, 2017: Inorganic Chemistry
Chao Zhuo, Yuehong Wen, Shengmin Hu, Tianlu Sheng, Ruibiao Fu, Zhenzhen Xue, Hao Zhang, Haoran Li, Jigang Yuan, Xi Chen, Xintao Wu
Enantioseparation is an integral process in the pharmaceutical industry, considering the ever-increasing demand for chiral medicine products. As a new material, porous metal-organic frameworks (MOFs) have shown their potential application in this field because their structures are easy to adjust and control. Though chiral recognition between racemic substrates and frameworks has made preliminary progress, discussions of their size-matching effects are rare. Herein with the help of channel-tunable homochiral MOFs (HMOFs), diols of different sizes have been separated in good enantiomeric excess (ee%)...
May 24, 2017: Inorganic Chemistry
Kyle Fulle, Liurukara D Sanjeewa, Colin D McMillen, Yimei Wen, Apeksha C Rajamanthrilage, Jeffrey N Anker, George Chumanov, Joseph W Kolis
Two terbium germanates have been synthesized via high-temperature and high-pressure hydrothermal synthesis with 20 M KOH as a mineralizer using Tb4O7 as a starting material. Tb13(GeO4)6O7(OH) crystallizes in trigonal space group R3̅, is built up of isolated GeO4 units, and contains a complex arrangement of terbium oxide polyhedra. K2TbGe2O7 is a terbium(4+) pyrogermanate that is isostructural with K2ZrGe2O7 and displays a rare stable Tb(4+) oxidation state in the solid state.
May 24, 2017: Inorganic Chemistry
Liyi Li, Jiangkun Cao, Bruno Viana, Shanhui Xu, Mingying Peng
The resistance to thermal quenching is an essential factor in evaluating the performance of luminescent materials for application in white light emitting diodes (WLEDs). In this work, we studied the site occupancy preference and thermal quenching of luminescence in β-Ca2P2O7:Bi(2+) red phosphor at low (10-300 K) and high temperatures (303-573 K). In β-Ca2P2O7, the host lattice has four different calcium sites, at which Bi(2+)dopant can be located. After comparing the change of bond energy when the Bi(2+) ions are incorporated into the four calcium sites, we found out that Bi(2+) would preferentially occupy the smaller energy variation sites Ci(2) and Ci(1) in this compound, which can be assigned to Bi(2) and Bi(1), respectively...
May 24, 2017: Inorganic Chemistry
Zhifu Liang, Marko Damjanović, Mritunjoy Kamila, Goulven Cosquer, Brian K Breedlove, Markus Enders, Masahiro Yamashita
Two double-decker complexes with annulene ligands functionalized with indolenine groups were synthesized and characterized. The position of the proton acting as a counterion on one of the four indolenine nitrogen atoms was determined by using DFT calculations. Deprotonation and protonation of the complex induced by adding a base and an acid, respectively, were monitored by using NMR spectroscopy. Moreover, a correlation among the degree of protonation of the complex, the opening of the hysteresis, and the slow relaxation time is discussed...
May 24, 2017: Inorganic Chemistry
Jin-Le Hou, Wen Luo, Yao Guo, Ping Zhang, Shen Yang, Qin-Yu Zhu, Jie Dai
A unique titanium oxo cluster with a ferrocene ligand was synthesized and characterized by single crystal X-ray analysis. Six ferrocene carboxylates coordinate to a D3d Ti6O6 core to be a redox active cluster 1, [Ti6O6(O(i)Pr)6(O2CFc)6]. An analogue 2, [Ti6O6(O(i)Pr)6(O2C(i)Bu)6], where the redox active ferrocene group is replaced by isobutyrate, is also reported as a contrast. The six ferrocene moieties in 1 are structurally identical to give a main redox wave at E1/2 = 0.62 V in dichloromethane investigated by cyclic voltammetry...
May 24, 2017: Inorganic Chemistry
Da Xie, Seyong Kim, Vikraant Kohli, Arnab Banerjee, Meng Yu, José S Enriquez, Jeffrey J Luci, Emily L Que
(19)F magnetic resonance imaging (MRI), an emerging modality in biomedical imaging, has shown promise for in vitro and in vivo preclinical studies. Here we present a series of fluorinated Cu(II)ATSM derivatives for potential use as (19)F magnetic resonance agents for sensing cellular hypoxia. The synthesized complexes feature a hypoxia-targeting Cu(2+) coordination core, nine equivalent fluorine atoms connected via a variable-length poly(ethylene glycol) linker. Introduction of the fluorine moiety maintains the planar coordination geometry of the Cu(2+) center, while the linker length modulates the Cu(2+/+) reduction potential, (19)F NMR relaxation properties, and lipophilicity...
May 24, 2017: Inorganic Chemistry
Joanna Palion-Gazda, Barbara Machura, Rafal Kruszynski, Thais Grancha, Nicolás Moliner, Francesc Lloret, Miguel Julve
The preparation and spectroscopic and structural characterization of three cobalt(II) complexes of formulas [Co(tppz)2](dca)2 (1), [Co(tppz)2][Co(NCS)4]·MeOH (2), and [Co(tppz)2][Co(NCO)4]·2H2O (3) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and dca = dicyanamide] are reported here. Compounds 1-3 have in common the presence of the cationic [Co(tppz)2](2+) entity where each mer-tridentate tppz ligand coordinates to the cobalt(II) ion equatorially through two pyridyl donors and axially via the pyrazine, completing the six-coordination...
May 22, 2017: Inorganic Chemistry
Congcong Shang, Romain Gautier, Tengfei Jiang, Eric Faulques, Camille Latouche, Michael Paris, Laurent Cario, Martine Bujoli-Doeuff, Stéphane Jobic
An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal-organic framework (MOF), (ZnC2O3H2)n, which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn-O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs)...
May 22, 2017: Inorganic Chemistry
Elena A Makarova, Yuriy V Zatsikha, Kelly M E Newman, Vinod K Paidi, Valeria A Beletsky, Johan van Lierop, Evgeny A Lukyanets, Victor N Nemykin
An unprecedented stable neutral radical nickel(II) complex of 3,5-bis(dimedonyl)azadiisoindomethene (1) was prepared by the direct reaction between 1,3-diiminoisoindoline and dimedone. A new radical complex 1 has an intense and narrow absorption at 1008 nm and can be reduced to a less stable anionic [1](-) with a typical aza(dibenzo)boron dipyrromethene (aza-BODIPY) UV-vis spectrum. Complex 1, along with two other colored condensation reaction products 2 and 3, was characterized by spectroscopy and X-ray crystallography, while the paramagnetic nature of 1 was probed by EPR and SQUID methods...
May 19, 2017: Inorganic Chemistry
Qi Wei, Jia-Jia Wang, Jie Zhang, Guo-Yu Yang
Two three-dimensional (3D) zeolitic open-framework aluminoborates (ABOs) [Zn(ma)(en)2][AlB5O10] (1) and [Zn(ma)(en)2][AlB6O11(OH)] (2) (ma = methylamine, en = ethylenediamine) were successfully made under solvothermal conditions, which represent the first examples using similar metal complex (MC) with mixed amines as the structure-directing agents in ABOs. Notice that the central atom in the MC is coordinated by mixed amines is uncommon. However, they exhibit distinctly different structures: 1 crystallizes in a centrosymmetric [Al(B5O10)]n(2n-) zeolitic framework built by pentaborate (B5O10) clusters and AlO4 tetrahedra, exhibiting a 4-connected cag topology, while 2 contains hexaborate (B6O11(OH)) clusters and AlO4 groups, further alternately joined to form a noncentrosymmetric [AlB6O11(OH)]n(2n-) zeolitic framework with 7-/9-, 8-/10-ring helical channels and large 13-ring channels, showing a dia topology...
May 19, 2017: Inorganic Chemistry
Haitao Li, Fang Guo, Meng Kou, Antonino Famulari, Qiang Fu, Javier Marti-Rujas
Gas-solid chemisorption of HCl and adsorption of MeOH/EtOH by nonporous chiral copper(II) coordination complexes 1·MeOH and 1″·MeOH occur in a cooperative and dynamic manner to give solvated second sphere adducts 1'·MeOH/EtOH. The chemisorption process involves dramatic atomic rearrangements in the crystalline state upon cleavage and formation of H-Cl, N-H, Cu-N, and Cu-Cl coordination and covalent bonds from the gas and solid state, respectively. Using mechanochemistry, the chloride-bridged coordination complex 1″·MeOH is selectively produced by means of a dehydrochlorination reaction, but not in solution in which a mixture of 1·MeOH and 1″·MeOH is obtained...
May 19, 2017: Inorganic Chemistry
Xiaodong Sun, Shuo Yao, Guanghua Li, Lirong Zhang, Qisheng Huo, Yunling Liu
A Zn4O clusters based flexible doubly interpenetrated metal-organic framework [(Zn4O)2(DCPB)6DMF]·2DMF·8H2O (JLU-Liu33, H2DCPB = 1,3-di(4-carboxyphenyl)benzene, DMF = N,N-dimethylformamide) with pcu topology has been solvothermally synthesized. Because of its flexible structure, JLU-Liu33 exhibits a breathing behavior upon N2 and CO2 adsorption at low temperature, and C2H6 and C3H8 adsorption at 273 and 298 K. Furthermore, by adopting the direct synthesis method, two isomorphic compounds-JLU-Liu33L and JLU-Liu33H-have been obtained by partial substituting Zn with different amounts of Co into the JLU-Liu33 framework...
May 19, 2017: Inorganic Chemistry
Kang-Yu Zou, Yi-Chen Liu, Yi-Fan Jiang, Cheng-Yan Yu, Man-Li Yue, Zuo-Xi Li
Herein three novel cobalt metal-organic frameworks (Co-MOFs) with similar ingredients, [Co(bib)(o-bdc)]∞ (1), [Co2(bib)2(m-bdc)2]∞ (2), and {[Co(bib)(p-bdc)(H2O)](H2O)0.5}∞ (3), have been synthesized from the reaction of cobalt nitrate with 1,4-bis(imidazol-1-yl)benzene (bib) and structure-related aromatic acids (1,2-benzenedicarboxylic acid = o-bdc, 1,3-benzenedicarboxylic acid = m-bdc, and 1,4-benzenedicarboxylic acid = p-bdc) by the solvothermal method. It is aimed to perform systematic research on the relationship among the conformation of benzoate acid, lattice dimension of Co-MOF, and pore diameter of MOF-derived carbon composite...
May 19, 2017: Inorganic Chemistry
Daniel Álvarez, Raúl Mera-Adasme, Lucía Riera, Gloria I Cárdenas-Jirón, Julio Pérez, Jesús Díaz, M Isabel Menéndez, Ramón López
Herein we present a theoretical study on the reaction of [Re(PPh2) (CO)3(phen)] (phen = 1,10-phenanthroline) and [Re(PPh2) (CO)3(bipy)] (bipy = 2,2'-bipyridine) toward methyl propiolate. In agreement with experimental results for the phen ligand, the coupling of the substituted acetylenic carbon with the nonsubstituted ortho carbon of the phen ligand is the preferred route from both kinetic and thermodynamic viewpoints with a Gibbs energy barrier of 18.8 kcal/mol and an exoergicity of 11.1 kcal/mol. There are other two routes, the insertion of the acetylenic fragment into the P-Re bond and the coupling between the substituted acetylenic carbon and a carbonyl ligand in cis disposition, which are kinetically less favorable than the preferred route (by 2...
May 18, 2017: Inorganic Chemistry
Cristina Femoni, Guido Bussoli, Iacopo Ciabatti, Marco Ermini, Mohammad Hayatifar, Maria C Iapalucci, Silvia Ruggieri, Stefano Zacchini
The reaction of [Rh7(CO)16](3-) with BiCl3 under N2 and at room temperature results in the formation of the new heterometallic [Bi@Rh12(CO)27](3-) cluster in high yields. Further controlled addition of BiCl3 leads first to the formation of the dimeric [(Bi@Rh12(CO)26)2Bi](5-) and the closo-[Bi@Rh14(CO)27Bi2](3-) species in low yields, and finally, to the [Bi@Rh17(CO)33Bi2](4-) cluster. All clusters were spectroscopically characterized by IR and electrospray ionization mass spectrometry, and their molecular structures were fully determined by X-ray diffraction studies...
May 18, 2017: Inorganic Chemistry
Sergey V Ovsyannikov, Elena Bykova, Anna Pakhomova, Denis P Kozlenko, Maxim Bykov, Sergey E Kichanov, Natalia V Morozova, Igor V Korobeinikov, Fabrice Wilhelm, Andrei Rogalev, Alexander A Tsirlin, Alexander V Kurnosov, Yury G Zainulin, Nadezda I Kadyrova, Alexander P Tyutyunnik, Leonid Dubrovinsky
We investigated the structural, vibrational, magnetic, and electronic properties of the recently synthesized CaCo3V4O12 double perovskite with the high-spin (HS) Co(2+) ions in a square-planar oxygen coordination at extreme conditions of high pressures and low temperatures. The single-crystal X-ray diffraction and Raman spectroscopy studies up to 60 GPa showed a conservation of its cubic crystal structure but indicated a crossover near 30 GPa. Above 30 GPa, we observed both an abnormally high "compressibility" of the Co-O bonds in the square-planar oxygen coordination and a huge anisotropic displacement of HS-Co(2+) ions in the direction perpendicular to the oxygen planes...
May 18, 2017: Inorganic Chemistry
Carolyn E Carr, Francesco Musiani, Hsin-Ting Huang, Peter T Chivers, Stefano Ciurli, Michael J Maroney
Escherichia coli RcnR (resistance to cobalt and nickel regulator, EcRcnR) is a metal-responsive repressor of the genes encoding the Ni(II) and Co(II) exporter proteins RcnAB by binding to PRcnAB. The DNA binding affinity is weakened when the cognate ions Ni(II) and Co(II) bind to EcRcnR in a six-coordinate site that features a (N/O)5S ligand donor-atom set in distinct sites: while both metal ions are bound by the N terminus, Cys35, and His64, Co(II) is additionally bound by His3. On the other hand, the noncognate Zn(II) and Cu(I) ions feature a lower coordination number, have a solvent-accessible binding site, and coordinate protein ligands that do not include the N-terminal amine...
May 18, 2017: Inorganic Chemistry
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