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  • 更新日期:2020-01-21
  • Catalytic Domino Annulations through η3‐Allylpalladium Chemistry: A Never‐Ending Story
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-20
    Yang Liu; Julie Oble; Alexandre Pradal; Giovanni Poli
    更新日期:2020-01-21
  • A Thiacalix Basket and Its Anion‐Dependent 2‐D and 3‐D Silver(I) Coordination Polymers via Exo‐Coordination
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-20
    Huiyeong Ju; In‐Hyeok Park; Eunji Lee; Chungsik Kim; Seulgi Kim; Shunsuke Kuwahara; Yoichi Habata; Shim Sung Lee
    更新日期:2020-01-21
  • High‐Pressure Synthesis of the Acentric Borate DyB5O8(OH)2
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-20
    Michael Zoller; Gunter Heymann; Andreas Saxer; Hubert Huppertz
    更新日期:2020-01-21
  • Selectively tunable domino reaction of 1,3‐diphenylpropane‐1,3‐dione on ethoxy‐silicon core
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-20
    Rózsa Szűcs; Csaba Fekete; Petra Bombicz; János Rochonczy; Ilona Kovács; László Nyulászi

    The reaction of (EtO) 3 SiCl with 1,3‐diphenylpropane‐1,3‐dione in dichloromethane yields in an ionic hexacoordinate compound featuring three chelating 1,3‐diphenylpropane‐1,3‐dionato ligands as proven by its X‐ray structure and multinuclear NMR studies in a fast domino reaction. With a proper selection of the solvent (toluene) and the reaction time the intermediates of the reaction sequence can be selectively obtained. With an excess of the starting chlorosilane and short reaction times the tetracoordinate silane can be obtained by the replacement of the chloro substituent. This compound shows a dynamic behavior according to its 13 C NMR spectrum, involving its pentacoordinate isomer, which is only slightly less stable, according to DFT calculations. The hemilabile ethoxy group can easily be replaced by a further 1,3‐diphenylpropane‐1,3‐dionato ligand yielding in the neutral hexacoordinate silane with two chelators and two ethoxy groups, as characterized by X‐ray crystallography and multinuclear NMR studies.

    更新日期:2020-01-21
  • Heterochiral or homochiral self‐assembly: Hg(II), Cd(II) and spontaneous resolution of Ag(I) complexes derived from a racemic bis(pyridyl) ligand
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-20
    Chao Huang; Yong-Jie Liu; Ya-Ting Chen; Dong Mei Chen; Bi-Xue Zhu

    A novel racemic bis(pyridyl) ligand ( rac ‐ L ) was designed and synthesized by Schiff condensation reaction. Five complexes, [Hg 2 ( L R )( L S )Cl 4 ]·2CH 3 CH 2 OH ( 1 ), [Cd( L R )( L S )Cl 2 ] n ( 2 ), {[Cd( L R )( L S )SO 4 (H 2 O)]·11H 2 O} n ( 3 ), {[Ag( L R ) 2 ]NO 3 ·CH 3 CN} n ( 4a ) and {[Ag( L S ) 2 ]NO 3 ·CH 3 CN} n ( 4b ) have been synthesized and characterized, respectively. The differently geometric features of the obtained complexes 1 ‐ 4 were determined by single‐crystal X‐ray diffraction. The crystal structures show that the self‐assembly with racemic ligands can lead to homochiral or heterochiral complexes, through self‐recognition or self‐discrimination of the ligand units. Complex 1 exists as a 26‐membered binuclear heterochiral macrocycle. Complexes 2 and 3 form 1D mesomeric looped chain coordination polymers with different heterochiral self‐assembly types. More interestingly, two novel 2D homochiral coordination polymers 4a and 4b were obtained as racemic conglomerates via spontaneous resolution. Furthermore, the thermal stabilities and luminescence properties of complexes 1 ‐ 4 were investigated.

    更新日期:2020-01-21
  • Biological evaluation of azo‐ and imino‐based carboxylate based triphenyltin(IV) compounds
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-19
    Anup Paul; Susanta Hazra; M. Fátima C. Guedes da Silva; Armando J. L. Pombeiro

    Azo (‐N=N‐)‐ and imino (‐C=N‐)‐carboxylate triphenyltin(IV) compounds are well known for their promising biological activities, and are usually synthesized by reacting triphenyltin(IV) compound (oxide, hydroxide or chloride) with a suitably substituted carboxylic acid, under appropriate conditions. Their biological properties are influenced by the type/position of the functional azo or imino group in the carboxylate ligand skeleton. They are very effective in anticancer studies, being often better than the standard drug cisplatin in terms of cytotoxicity. A few of the azo‐appended carboxylate triphenyltin(IV) compounds also display anti‐bacterial, anti‐fungal and anti‐diabetic activities. The present manuscript highlights the syntheses, structures and biological ( i.e. , anti‐cancer, anti‐bacterial, anti‐fungal and anti‐diabetic) activities of such triphenyltin(IV) compounds.

    更新日期:2020-01-21
  • 1D MOF‐Derived N‐Doped Porous Carbon Nanofibers Encapsulated with Fe3C Nanoparticles for Efficient Bifunctional Electrocatalysts
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-17
    Jiang-Tao Liu; Yan Xie; Qiang Gao; Fu-Hu Cao; Ling Qin; Zhen-Yu Wu; Wang Zhang; Hao Li; Chuan-Ling Zhang

    A facile yet efficient approach is introduced to rationally integrate Fe 3 C nanoparticles with Fe‐N‐doped mesoporous carbon nanofibers (denoted as Fe 3 C@FeN@CNF) by the direct‐electrospinning technique and a subsequent calcination process. Benefiting from the unique one‐dimensional structure with high porosity and the synergies among the active sites of Fe‐Nx, N‐C and graphitic carbon encapsulated Fe 3 C/Fe nanoparticles, the hierarchically structured Fe 3 C@FeN@CNF show enhanced electrocatalytic activity and durability for oxygen reduction and oxidation reactions, and comparable to that of commercialized Pt/C electrocatalyst. Significantly, the as‐fabricated Fe 3 C@FeN@CNF composite shows higher electrochemical performances than Pt/C in the Zn‐air battery.

    更新日期:2020-01-21
  • Corner‐ and Side‐Opened Cage Silsesquioxanes: Structural Effects on the Materials Properties
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-16
    Hiroaki Imoto; Yukiho Ueda; Yuri Sato; Masashi Nakamura; Koji Mitamura; Seiji Watase; Kensuke Naka

    Open‐cage silsesquioxane, in which traditional closed‐cage silsesquioxane is partially hydrolyzed, is a promising class of building blocks for constructing organic‐inorganic hybrid. It has advantages in high thermal stability, low crystallinity, transparency, designability, etc. Although the structural effects of closed‐cage silsesquioxanes have been elucidated in detail so far, those of open‐cages have never been studied. Herein, we synthesized corner‐ and side‐opened cage silsesquioxanes having carbazole units at the open moieties. The former was amorphous in the solid state and polymer matrix, while the latter formed crystalline structures. These different packing structures caused significant difference in the performance as an emission layer of organic light emitting device.

    更新日期:2020-01-17
  • Fine‐Tuning: Advances in Chlorine‐Free Blue‐Light‐Generating Pyrotechnics
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-15
    Johann Glück; Thomas M. Klapötke; Teresa Küblböck
    更新日期:2020-01-16
  • Synthesis and Photochemical Properties of Manganese(I) Tricarbonyl Diimine Complexes Bound to Tetrazolato Ligands
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-15
    Matthew J. Stout; Alessandra Stefan; Brian W. Skelton; Alexandre N. Sobolev; Massimiliano Massi; Alejandro Hochkoeppler; Stefano Stagni; Peter V. Simpson
    更新日期:2020-01-16
  • 更新日期:2020-01-15
  • Synthesis and Characterization of Cationic Pt(II) Complexes Combining Two Chelating Ligands in Their Structures
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-15
    Ondrej Barta; Piermaria Pinter; Ivana Cisarova; Thomas Strassner; Petr Stepnicka

    A series of cationic Pt(II) complexes with chelating bis‐carbene and P,P‐ or P,S‐ligands, viz . [(C^C)Pt(X^Y)][BF 4 ] 2 ( 2a‐e ), where C^C = methylenebis(3‐methyl‐1 H ‐imidazol‐1‐yl‐2‐ylidene), and X^Y = Ph 2 PCH 2 CH 2 PPh 2 (dppe) ( a ), Ph 2 P(CH 2 ) 3 PPh 2 (dppp) ( b ), 1,2‐(Ph 2 P) 2 C 6 H 4 (dppbz) ( c ), [Fe(η 5 ‐C 5 H 4 PPh 2 ) 2 ] (dppf) ( d ), and Ph 2 PCH 2 CH 2 SPh ( e ), were synthesized and structurally characterized by NMR and MS spectroscopy and by single‐crystal X‐ray diffraction analysis. Photophysical measurements showed that these compounds were non‐emissive at room temperature. However, when cooled to 77 K, compounds 2a , 2b and 2c showed weak luminescence in the near UV region with emission maxima in the 380‐395 nm range.

    更新日期:2020-01-15
  • Cooperative Donor‐Acceptor Interactions in Stabilizing Carbene‐Borane and Carbene‐Alane Compounds: A Theoretical Insight
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-14
    Sayan Dutta; Sriman De; Sanjoy Bose; Eti Mahal; Debasis Koley

    Density functional theory calculations have been performed to elucidate the electronic structure and bonding scenario in various carbene‐borane (LBX3) and carbene‐alane (LAlX3) compounds (X = ‐H, ‐Me, ‐Cl, ‐Ph, ‐C6F5). We have performed extended transition state (ETS) analysis to reveal the nature of the donor‐acceptor bonds (Ccarb−E; E = B, Al) and also for the assessment of the intrinsic donor‐acceptor strength in this class of compounds. Our computations suggest that the Ccarb−Al bonds in all the LAlX3 adducts have substantially higher electrostatic nature than covalent character. Conversely, the nature of the Ccarb−B bonds in LBX3 have a strong dependence on the electronic nature of both carbene and borane. Moreover, unlike alanes in LAlX3, the intrinsic Lewis acid strength of the boranes in LBX3 has a strong dependence on the electronic nature of the carbenes. We have also explored the correlation of the interaction energies (ΔEint) with various bonding parameters i.e. geometrical and Natural bond orbital (NBO) parameters of LEH3. Furthermore, natural orbital for chemical valence (NOCV) calculations are performed to have a qualitative understanding of the relative σ‐donating and π‐accepting abilities of the carbenes in LEH3. Additionally, we have investigated the abilities of carbenes to activate the B−H bonds in BH3 and pinacolborane. ETS analysis shows a strong dependence of the B−H activation barriers on the distortion energies of both carbene and borane fragments.

    更新日期:2020-01-15
  • (Electro‐)chemical Splitting of Dinitrogen with a Rhenium Pincer Complex
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-14
    Richt S. van Alten; Florian Wätjen; Serhiy Demeshko; Alexander J. M. Miller; Christian Würtele; Inke Siewert; Sven Schneider

    The splitting of N 2 into terminal well‐defined, terminal nitride complexes is a key reaction for nitrogen fixation at ambient conditions. In continuation of our previous work on rhenium pincer mediated N 2 splitting, nitrogen activation and cleavage upon (electro)chemical reduction of [ReCl 2 ( L 2)] ( L 2 = N(CHCHPtBu 2 ) 2 ‐ ) is reported. The electrochemical characterization of [ReCl 2 ( L 2)] and comparison with our previously reported platform [ReCl 2 ( L 1)] ( L 1 = N(CH 2 CH 2 PtBu 2 ) 2 ‐ ) provides mechanistic insight to rationalize the dependence of nitride yield on the reductant. Furthermore, the reactivity of N 2 derived nitride complex [Re(N)Cl( L 2)] with electrophiles is presented.

    更新日期:2020-01-15
  • Dendrimer‐Based Gold Nanostructures for SERS Detection of Pesticides in Water
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-14
    Tiago Fernandes; Sara Fateixa; Helena I. S. Nogueira; Ana L. Daniel‐da‐Silva; Tito Trindade
    更新日期:2020-01-14
  • N‐Heterocyclic Carbene and Cyclic (Alkyl)(amino)carbene Complexes of Titanium(IV) and Titanium(III)
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-14
    Günther Horrer; Mirjam J. Krahfuß; Katharina Lubitz; Ivo Krummenacher; Holger Braunschweig; Udo Radius
    更新日期:2020-01-14
  • Dinuclear Cu(II) molecules exhibiting reversible photochromism
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-13
    Jorge Salinas-Uber; Leoní A. Barrios; Marta Estrader; Olivier Roubeau; Guillem Aromi

    We present here the design and preparation of several discrete coordination complexes exhibiting two Cu(II) ions separated by a dithienylcyclopentene as a photoswitchable spacer, proposed as models of molecular √SWAP quantum gates. These models use the two Cu(II) ions as realizations of qubits and the spacer as a light switch intended to trigger the gate by reversibly undergoing a ring closing isomerization. For this, a dicarboxylate species with a central diarylethene, H 2 L1, has been used, together with bipyridine or phenatroline as capping ligands. Also, a new dinucleating ligand containing the photoactive moiety in between to tridentate coordinating pockets, H 4 L2, has been designed and prepared for the same purpose. The four complexes have been characterized by single crystal X‐ray diffraction. Three of them exhibit reversible photoswitching in solution.

    更新日期:2020-01-14
  • Total Structure Determination of Pt1Ag9[P(Ph‐F)3]7Cl3 Nanocluster
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-13
    Wenjing Sun; Shan Jin; Wenjun Du; Xi Kang; Along Chen; Shuxin Wang; Hongting Sheng; Manzhou Zhu

    An atomically precise luminescent Pt‐Ag alloy nanocluster (Pt 1 Ag 9 [P(Ph‐F) 3 ] 7 Cl 3 (P(Ph‐F) 3 = tris(4‐fluorophenyl) phosphine))(Pt 1 Ag 9 for short) was synthesized. Its structure was determined by single crystal X‐ray diffraction (SCXRD) and further confirmed by electrospray ionization mass spectrometry (ESI‐MS), X‐ray photoelectron spectrospray (XPS) and Nuclear Magnetic Resonance (NMR) measurements. Surprisingly, the Pt 1 Ag 9 kernel can be regarded as the icosahedral Pt 1 Ag 12 kernel missing three Ag atoms, accompanied with no structural reformation in this nanocluster. And the central Pt atom was exposed and capped by phosphine ligand directly in contrast with other reported Pt‐Ag alloy nanoclusters. Upon excitation at 435 nm, the emission spectra of Pt 1 Ag 9 nanocluster exhibits a prominent peak at 662 nm (quantum yield QY=0.6658%) with a very short photoluminescence lifetime (0.357 ns). This work provides a deep understanding of the structure and properties of Pt‐Ag alloy nanoclusters.

    更新日期:2020-01-13
  • Synthesis of a T‐Shaped Cobalt(I) Complex and its Dinitrogen Adduct
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-12
    Corey Sanz; Carolin Stein; Michael D. Fryzuk

    The coordination chemistry of the new NNP pincer ligand framework (QuiNacNacP) is explored with cobalt. Upon treatment of the cobalt(II) complex Co[QuiNacNacP]Cl with KC 8 , the formation of cobalt(I) dinitrogen complex Co[QuiNacNacP]N 2 was observed. Co[QuiNacNacP]N 2 crystallizes as a square planar (S = 0) complex with an essentially unactivated N 2 ligand. In solution, the dinitrogen complex is in equilibrium with the paramagnetic T‐shaped complex Co[QuiNacNacP] (S = 1). The ability of Co[QuiNacNacP]Cl to act as a catalyst precursor in the reductive silylation of dinitrogen was also briefly explored. Reaction of ~1000 equivalents KC 8 with ~1500 equivalents Me 3 SiCl (relative to Co[QuiNacNacP]Cl ) under 1 atm of N 2 furnished roughly 40 equivalents of N(SiMe 3 ) 3 .

    更新日期:2020-01-13
  • 更新日期:2020-01-10
  • 更新日期:2020-01-10
  • Dynamic Gold(I) Complexes of Hexa‐tert‐butyl‐octaphosphane
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-10
    Toni Grell; Evamarie Hey-Hawkins

    A facile synthesis for {cyclo‐(P4tBu3)}2 (1) is reported making the phosphane available for follow‐up chemistry. Octaphosphane 1 reacts with [AuCl(tht)] (tht = tetrahydrothiophene) to give a monometallic ([AuCl(1‐κ2P2,P4‘)], 2), bimetallic ([(AuCl)2(1‐κ2P2,P4‘,κP2‘)], 3) and trimetallic complex ([(AuCl)3(1‐κ2P2,P4‘,κP2‘,κP4)], 4) in which up to four phosphorus atoms of the ligand are involved in coordination. In each of these complexes one gold(I) atom is chelated in an unusual [2+1] coordination mode which undergoes a rapid exchange between both donor atoms in solution. This mode of coordination in combination with the flexibility of the phosphane ligand moreover gives rise to an interesting dynamic behavior of the monometallic complex 2 which was elucidated by NMR spectroscopy, X‐ray crystallography and DFT calculations.

    更新日期:2020-01-10
  • Electrocatalytic Hydrogen Evolution of Cobalt and Free Base Triaryl Corrole Bearing Hydroxyethyl Amino Groups
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-09
    Ying Chen; Qi-Hang Fan; Md Sahadat Hossain; Shu-Zhong Zhan; Hai-Yang Liu; Li-Ping Si

    Four free base corroles (F 15 CCo, F 12 CCo, F 10 CCo, F 12 CCo) and their cobalt(III) complexes were used as homogeneous electrocatalysts for hydrogen evolution using acetic acid, trifluoroacetic acid and water as proton sources. Free base corrole was firstly reported as electrocatalyst for H 2 evolution. The results showed free base corrole was active in electrocatalytic hydrogen evolution reaction (HER) in trifluoroacetic acid. And cobalt(III) corroles bearing hydroxyethyl amino groups were more efficient in HER as compared to their benchmark corroles. The catalytic active species of four tested cobalt(III) corroles were Co II ‐H in acetic acid/dimethylformamide solvent. In water solution, both Co III ‐H and Co II ‐H may be involved in HER. Interestingly, when trifluoroacetic acid was used as proton source, Co III ‐H was the mainly active intermediate for F 12 CCo and F 8 CCo, and Co II ‐H for F 15 CCo and F 10 CCo, respectively. As for free base corrle, ( • Cor)H 4 and [( • Cor)H 3 ] ‐ were the catalytic active species.

    更新日期:2020-01-10
  • Transition metal complexes promoted activation and functionalization of dinitrogen in the presence of molecular hydrogen
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-09
    Chinnappan Sivasankar; Packirisamy Kuzhalmozhi Madarasi; Masilamani Tamizmani

    The quest for functionalization of dinitrogen is a challenging task for decades owing to its high redox potential. The transition metal dinitrogen complex made by Allen and Senoff provoked the researchers to functionalize dinitrogen and produce ammonia either stoichiometrically or catalytically using mild reaction conditions. Predominantly there are two methodologies available for the functionalization of dinitrogen. In the first methodology, proton and electron sources are used for the functionalization of dinitrogen, which is similar to the biological nitrogen fixation. In the second methodology, molecular hydrogen is used for the functionalization of dinitrogen, which is similar to Haber – Bosch process. Nonetheless Haber – Bosch process is the only successful industrial methodology for the production of ammonia. However, this methodology is highly energy consuming. Hence, there is a necessity for a practically viable homogeneous catalyst that could replace the heterogeneous Haber – Bosch process and thus conserve energy. However, there are very less reports on the utilization of molecular hydrogen for the functionalization of dinitrogen owing to the difficulty in handling dinitrogen and molecular hydrogen in a single reactor because the relatively more acidic molecular hydrogen could replace the dinitrogen. Nonetheless, only the proton part of H2 has been used and yet to utilize the hydride part of H2 in the near future. This review article describes the various endeavor made by the researchers to utilize the molecular hydrogen for the functionalization of dinitrogen.

    更新日期:2020-01-10
  • Coexistence of Metal Phthalocyanine and Fullerene C60 Anions in Mixed {cryptand[2.2.2](Na+)}x(MPc)–x‐1·(C60) – Salts (M = CoI, VIVO, x = 2 and 1.5)
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-09
    Dmitri V. Konarev; Mikhail G. Andronov; Alexey V. Kuzmin; Salavat S. Khasanov; Rimma N. Lyubovskaya
    更新日期:2020-01-09
  • A new hexa‐TiIV‐substituted sandwich‐type polyoxotungstate: hydrothermal synthesis, structure and oxidative decontamination of chemical warfare agent simulant
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-09
    Yue-Lin Wang; Jun-Jun Sun; Dan Qin; Guo-Yu Yang

    A new hexa‐Ti IV ‐substituted sandwich‐type silicotungstate, Na 2 (H 2 enMe) 4 [Ti 6 (μ‐O) 9 (A‐α‐SiW 9 O 34 H 2 ) 2 ]·16H 2 O ( 1 , enMe = 1,2‐diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT‐IR spectroscopy, elemental analysis, thermogravimetric analysis, single‐crystal and powder X‐ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A‐α‐SiW 9 O 34 ] 10‐ Keggin moieties sandwiching a trigonal‐prismatic [Ti 6 (μ‐O 9 )] 6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES), using H 2 O 2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2‐chloroethyl ethyl sulfoxide (CEESO) with 100% selectivity. In addition, 1 exhibits good stability and recyclability.

    更新日期:2020-01-09
  • Role of the main and auxiliary ligands in the nuclearity of Cu‐Ln complexes
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-09
    Jean-Pierre Costes; Maria-Jesus Rodriguez Douton; Sergiu Shova; Laure Vendier

    Trianionic ligands with an inner N 2 O 2 , an outer O 2 O 2 or O 2 O coordination site and an oxygen atom coming from an amide function not involved in these sites yield dinuclear Cu‐Ln complexes that self‐assemble into tetranuclear species with an alternate arrangement of Cu and Ln ions. This alternate Cu‐Gd arrangement impedes Cu‐Cu and Gd‐Gd interactions that could be antiferromagnetic and favours presence of ferromagnetic Cu‐Gd interactions whose strength depends on the nature of the bridge, phenoxo bridge made of a single oxygen atom or amidato bridge made of three NCO atoms. Depending on the ligands the phenoxo bridges can be single (CuOGd) or double (CuO 2 Gd) while the amidato one is always a single (CuNCOGd) bridge. A particular complex involving a trinuclear Cu‐Gd‐Cu arrangement through two amidato bridges confirms that the Cu‐Gd interaction through the amidato bridge is always weaker than the interaction through the phenoxo bridge. It has been possible to obtain complexes with an alternate Cu‐Gd arrangement involving more than two Cu‐Gd entities when two amidato bridges are present. These two amidato bridges may come from a main ligand, as in the case of tetraanionic ligands possessing two amide functions, or from two different ligands containing one amide function that are assembled by a Gd ion through their phenoxo functions. Note that the presence of auxiliary chelating ligands only yields tetranuclear species, whatever the number of amide functions

    更新日期:2020-01-09
  • Switchable Dielectric Behavior and Order‐disorder Phase Transition in a New Organic‐inorganic Hybrid Compound: (CH3NH3)4[InCl6]Cl
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Min Li; Guan-Cheng Xu; Wen-Bo Xin; Yin-Qiang Zhang

    A new organic‐inorganic phase transition material (CH3NH3)4[InCl6]Cl (1), has been successfully synthesized and characterized. The compound undergoes a reversible first‐order phase transition at Curie temperature Tc=284 K, accompanied with a wide hysteresis of 12 K, which investigated by differential scanning calorimetry (DSC). The temperature dependence of the dielectric permittivity discloses an obvious step‐like dielectric anomaly. Single crystal X‐ray diffraction reveals that the order‐disorder transition of the [InCl6]3‐ anion and the methylammonium cation were the main factor drove the phase transition from high temperature phase with the space group P2/m to low temperature phase with the space group P2/n. This finding indicates that In‐based organic–inorganic hybrids compounds can be used to build phase transition materials, which broaden the way for exploring dielectric switching materials.

    更新日期:2020-01-09
  • 更新日期:2020-01-08
  • Decorated Tetrathiafulvalene‐Based Ligands: Powerful Chemical Tools for the Design of Single‐Molecule Magnets
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Olivier Cador; Boris Le Guennic; Lahcène Ouahab; Fabrice Pointillart
    更新日期:2020-01-08
  • Highly Efficient Extraction of Trivalent f‐Cations Using Several N‐Pivot Tripodal Diglycolamide Ligands in an Ionic Liquid: The Role of Ligand Structure on Metal Ion Complexation
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Seraj A. Ansari; Prasanta K. Mohapatra; Parveen K. Verma; Andrea Leoncini; Ashok K. Yadav; Shambhu N. Jha; Dibyendu Bhattacharyya; Jurriaan Huskens; Willem Verboom
    更新日期:2020-01-08
  • Addition of Re‐Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Daniel Álvarez; Jesús Díaz; M. Isabel Menéndez; Ramón López
    更新日期:2020-01-08
  • Homopolyatomic Chalcogen Radical Cations of Selenium and Tellurium
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Carsten Jenne; Marc C. Nierstenhöfer
    更新日期:2020-01-08
  • Synthesis of BiOF/TiO2 Heterostructures and Their Enhanced Visible‐Light Photocatalytic Activity
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Maryline Nasr; Wenshi Huang; Carla Bittencourt; Dandan Cui; Ying Sun; Lei Wang; Nathalie Gaillard Caperaa; Yuping Ning; Ping Song; Pierre Bonnet; Cong Wang
    更新日期:2020-01-08
  • The NpV and PuV Carbonate Systems: Thermodynamics and Coordination Chemistry
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Jean Aupiais; Jean‐Charles Alexandre; Rémi Sicre; Bruno Siberchicot; Sylvain Topin; Philippe Moisy; Nicolas Dacheux
    更新日期:2020-01-08
  • Effect of Cu Preferential Orientation on the Microstructure and Properties of Anodized CuxO Films
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Zhaoqing Gao; Jinwei Cao; Chen Wang; Yinbo Chen; Hussain Muhammad Muzammal; Weiqiang Wang; Hao Sun; Haitao Ma; Yunpeng Wang
    更新日期:2020-01-08
  • The Facile Synthesis of Lithium 2‐R‐Hydroquinolinide Complexes and Their High Activity toward ROP of ε‐Caprolactone
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Ziyao Fan; Peng Wang; Chen Wu; Zhimin Liu; Xia Chen

    Four lithium 2‐R‐hydroquinolinide complexes [1‐(2‐(R)‐C 9 H 7 )NLi•THF 2 ] 2 ( 1 R = Me, 2 R = n Bu) and [1‐(8‐(Me)‐2‐(Bu n )‐C 9 H 6 )NLi•X] 2 ( 3 X = THF, 4 X = Et 2 O) were prepared by the nucleophilic addition reaction of quinoline and 8‐methylquinoline with MeLi or Bu n Li, respectively. All complexes have been characterized through NMR spectroscopy. Complexes 2 ‐ 4 were determined by X‐ray crystallography. Interestingly, Li atom in 1 and 2 is tetracoordinate, whereas Li atom in 3 and 4 is three‐coordinate. All these complexes showed super‐high activity for the ring‐opening polymerization (ROP) of ε ‐caprolactone in both the absence and presence of BnOH at 35 °C in CH 2 Cl 2 . By the 1 ‐ 4 catalytic systems with or without BnOH as a co‐initiate, the ROP of ε ‐CL proceeded well in a living manner evidenced by the predictable molecular weights, narrow molecular weight distributions and kinetic studies. MALDI‐TOF MS analysis revealed that the resultant PCL showed the cyclic structure in the absence of BnOH and the BnO ‐ capped linear nature was observed in the presence of BnOH.

    更新日期:2020-01-08
  • Bimetallic Ag‐Au nanoparticles inside mesoporous titania thin films: synthesis by photoreduction, and galvanic replacement and catalytic activity
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Rusbel Coneo Rodríguez; Horacio Troiani; Sergio E. Moya; Mariano M. Bruno; Paula Cecilia Angelomé

    In this work, the synthesis and catalytic activity of bimetallic Ag‐Au nanoparticles (NPs) supported in TiO 2 mesoporous thin films (MTF) are presented. The composite materials were obtained through a two‐step procedure, performed at room conditions. In the first step, Ag NPs were grown inside the MTF by photoreduction. Then, a galvanic replacement reaction with Au was carried out, yielding the bimetallic NPs. The composites were characterized by UV–vis spectroscopy, transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and X‐ray reflectometry (XRR), which show that the alloyed Ag‐Au NPs are present inside the mesopores. Moreover, Ag and Au composition relationship can be controlled by adjusting the reaction times of the photoreduction and galvanic replacement reactions, respectively. Pores remain accessible after NPs synthesis, a feature that ensures their possible applications in any device that requires the contact between the NPs and the medium. Catalytic activity of the composites towards 4‐nitrophenol reduction by sodium borohydride was evaluated. Although all the bimetallic systems exhibit improved catalytic properties in comparison with the monometallic Ag composite, the sample with lower Au‐Ag relationship is the most effective. For the first time, to the best of our knowledge, bimetallic Au‐Ag NPs are encapsulated inside mesoporous TiO 2 films, paving the way towards a wide variety of applications.

    更新日期:2020-01-08
  • Dinitrogen Activation by a Titanium/Ruthenium Heteromultimetallic Hydride Complex
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-08
    Takanori Shima; Zhaomin Hou

    A titanium/ruthenium heteromultimetallic polyhydride complex [(Cp’Ti) 2 (Cp*Ru) 2 ( μ ‐H) 6 ] ( 3 ) (Cp’ = C 5 Me 4 SiMe 3 , Cp* = C 5 Me 5 ) was obtained from the reaction of [Cp’Ti(CH 2 SiMe 3 ) 3 ] ( 1 ) with [Cp*Ru( μ ‐H) 4 RuCp*] ( 2 ) under H 2 . Complex 3 can readily react with N 2 to give an imido/nitrido complex [(Cp’Ti) 2 (Cp*Ru) 2 ( μ ‐NH)( μ ‐N)( μ ‐H) 3 ] ( 4 ) via N–N bond cleavage and N–H bond formation. The result demonstrates that the heteromultimetallic hydride complexes can serve as a platform for dinitrogen activation.

    更新日期:2020-01-08
  • Atomic Platinum Anchored on Fe‐N‐C Material for High Performance Oxygen Reduction Reaction
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-07
    Ying Sha; Jiapeng Ji; Siyuan Li; Xuehui Gao; Bingkai Zhang; Min Ling; Chengdu Liang; Zhan Lin
    更新日期:2020-01-07
  • Synthesis of N,P‐Disecondary o‐Arylphosphanylanilines via o‐R1NHC6H4P(R)O2Et Precursors and Preliminary Study of Cyclocondensations with (EtO)3CH/NH4PF6
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-07
    Bhaskar R. Aluri; Mohammed Ghalib; Peter G. Jones; Holm Frauendorf; Joachim W. Heinicke
    更新日期:2020-01-07
  • Dinitrogen Activation and Functionalization with Chromium
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-07
    Alexander Kendall; Michael Thomas Mock

    The study of metal‐dinitrogen complexes has lent valuable insight into the nature of dinitrogen (N2) reduction to ammonia (NH3), known as “nitrogen fixation”. Even so, understanding this difficult transformation continues to be an elusive goal for chemists. The N2 chemistry of chromium (Cr) is exceptional for its diversity, rarity, and richness of depth. Hans Karsch opined in 1977 that “Almost all transition metals are known to form complexes with molecular nitrogen, but in the case of some metals ‐ notably chromium ‐ the examples are few and far between”. Although that sentiment hasn’t changed much in 42 years, recent advances in the field of Cr‐N2 chemistry have begun to illuminate that elusive relationship. Herein we cover the theory and experimental basis for chromium’s coordination, activation, reduction, and catalysis of N2 to NH3. A emphasis will be placed on work towards understanding catalytic systems for chromium mediated dinitrogen reduction.

    更新日期:2020-01-07
  • Development of SBU‐based mechanochemical approach for drug‐loaded MOFs
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-07
    Jan Nawrocki; Daniel Prochowicz; Andrzej Wiśniewski; Iwona Justyniak; Piotr Goś; Janusz Lewinski

    Metal−organic frameworks (MOFs) have attracted a great deal of attention in the areas of biomedicine due to their versatile porous structures and potentially ideal vehicle with loading bioactive molecules, and controlling to release small molecules. Current approaches for encapsulation of drug molecules in MOFs are usually based on multistep wet processes. We report here a novel simple and rapid solid‐state process that combines the mechanosynthesis of HKUST‐1 and the encapsulation of ibuprofen (rac‐IBU‐H), as a model drug molecule, in one‐pot reaction involving a pre‐assembled [Cu2(rac‐IBU)4]·2DMF cluster. The ibuprofen‐loaded MOF composite (with 58.5 wt% loading capacity) was also studied as a drug delivery carrier system in phosphate buffered saline (PBS) solution at 37°C.

    更新日期:2020-01-07
  • Phenoxylation of Alkynes Through Mono‐ and Dual‐Activation using Group 11 (Cu, Ag, Au) Catalysts
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-06
    Miguel Ramos; Jordi Poater; Nery Villegas-Escobar; Martí Gimferrer; Alejandro Toro-Labbé; Luigi Cavallo; Albert Poater

    NHC‐gold(I) based catalysts have displayed outstanding results toward hydroalkoxylation of terminal and internal alkynes in solvent‐free conditions and using low catalyst loadings. It has been demonstrated that in the hydrophenoxylation reaction the gold complex is composed by two moieties that determine the rate of the reaction by activating both substrates synergistically, i.e. [Au(OR)(NHC)] and [Au(η 2 ‐alkyne)(NHC)] + . Then, these bimetallic systems act cooperatively toward hydroalkoxylation reaction. Herein, density functional theory studies were carried out to get insights on the mechanism of hydrophenoxylation. The rate‐determining step, which corresponds to the formation of the C(alkyne)–O(alcohol) bond between [Au(OR)(NHC)] and [Au(η 2 ‐alkyne)(NHC)] + , was studied using energy decomposition analyses (EDA). It was found that the C–O bond shows strong electrostatic and orbital interactions between both fragments in the homobimetallic, heterobimetallic and monogold mechanisms. Moreover, the analyses were expanded to copper and argentum, and the steric sensibility was also studied through the use of different NHC ligands, including IMes, IMe, SIMes, IPr, and IPr*, that differ on their steric demand.

    更新日期:2020-01-07
  • Exploring the Reactivity and Biological Effects of Heteroleptic N‐Heterocyclic Carbene Gold(I)‐Alkynyl Complexes
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-03
    Jens Oberkofler; Brech Aikman; Riccardo Bonsignore; Alexander Pöthig; James Platts; Angela Casini; Fritz E. Kühn
    更新日期:2020-01-04
  • 更新日期:2020-01-04
  • In water Markovnikov hydration and one‐pot reductive hydroamination of terminal alkynes under Ruthenium nanoparticle catalysis
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-03
    Caterina Risi; Elena Cini; Elena Petricci; Simone Saponaro; Maurizio Taddei
    更新日期:2020-01-04
  • Enhancement of Selective Fixation of Dinitrogen to Ammonia under Modal Strong Coupling Conditions
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-03
    Tomoya Oshikiri; Xu Shi; Hiroaki Misawa

    The production of ammonia from atmospheric nitrogen and water using sunlight is an important way to obtain ammonia as an energy carrier and is a new paradigm for achieving a low‐carbon and sustainable‐energy society. In this study, we attempted to enhance the ammonia photosynthesis efficiency both by increasing the electron supply using a novel photoanode composed of Au film, TiO 2 , and Au‐NPs (ATA) with hybrid energy states due to modal strong coupling and by increasing the surface area of the Zr cathode. We investigated the key properties of this hybrid mode‐assisted NH 3 photosynthesis using two‐electrode systems combining photoanodes and cathodes by performing photoelectrochemical measurements and product analysis. We found that the ATA structure has high absorptivity and enhances the quantum efficiency of ammonia photosynthesis and the surface area available to adsorb N 2 on the Zr cathode is a critical factor for enhancing the reaction rate.

    更新日期:2020-01-04
  • Homoleptic zinc–catalyzed hydroboration of aldehydes and ketones in the presence of HBpin
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-02
    Gobbilla Sai Kumar; Adimulam Harinath; Rajrani Kawaria; Tarun Kanti Panda

    Here, we report the reaction between N ‐phenyl‐ o ‐phenylenediamine and pyrrole‐2‐carboxaldehyde to afford the N ‐phenyl‐ o ‐phenyl‐enediiminopyrrole ligand { L‐H2 } in quantitative yield. A one‐pot reaction between { L‐H2 } and diethylzinc (ZnEt 2 ) in a 2:1 ratio afforded the homoleptic zinc metal complex [ {L‐H} 2 Zn ] ( 1 ). The solid‐state structures of ligand { L‐H2 } and zinc complex 1 were confirmed using X‐ray crystallography. Further, complex 1 was used for chemoselective hydroboration of aldehydes and ketones in the presence of pinacolborane (HBpin) at ambient temperature to produce the corresponding boronate esters in high yield.

    更新日期:2020-01-04
  • (Photo)Thermal Stimulation of Functional Dithiolene Complexes in Soft Matter
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-02
    Franck Camerel; Marc Fourmigue

    Square‐planar bis(dithiolene) complexes are characterized with a planar delocalized structure and a strong and tunable Near Infra‐Red (NIR) absorption; they are highly stable under laser irradiation and their conversion efficiency (light to heat) reaches up to 40‐50%. Their involvement in soft matter, namely liquid crystals, gels and nanoparticles, opens many possibilities to control the actual state of a material, particularly under light irradiation. Thus, liquid crystalline phases can easily be modified, (i) with temperature to modulate the extended of magnetic interactions of paramagnetic complexes, or (ii) under laser irradiation to unravel these remarkable photothermal properties, toward the development of light‐responsive materials. Dithiolene complexes can be also functionalized to produce very effective gelation agents, while the photothermal effect can be used to destabilize at will their supramolecular organization. Besides photothermal therapy, photo‐controlled drug delivery and bioimaging were also considered to develop new therapeutic agents by combining chemotherapy and phototherapy. Thus, hydrophobic complexes were accordingly designed for their encapsulation in block copolymer nanoparticles for photothermal therapy and photo‐controlled drug delivery under laser irradiation. This class of complexes can be also used as exogenous contrast agents for photoacoustic bioimaging.

    更新日期:2020-01-02
  • Synthesis, Structure, and Characterization of Variable Chains in a Series of Transition Metal Coordination Compounds
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-02
    Jungjoo Kim; Hongil Jo; Sung Won Yoon; Min Hyung Lee; Woo Jae Choi; Kwang-Yong Choi; Kang Min Ok

    Five new transition metal coordination polymers, [Zn 3 ( bipy )( TC ) 6 ] ( 1 ), [Co 3 ( bipy )( TC ) 6 ] ( 2 ), [Co( bipy )( TC ) 2 ] ( 3 ), [Cd( bipy )( TC ) 2 ] ( 4 ), and [Cu 2 ( bipy )( TC ) 4 ] ( 5 ) ( bipy = 4,4’‐bipyridine; TC = 3‐thiophenecarboxylate) with chain structures were solvothermally synthesized in high yields under mild reaction conditions. While compounds 1 , 2 , and 3 reveal peddle wheel‐like chain structures, compounds 4 and 5 exhibit ladder‐like chain backbones. The organic bipy ligand was utilized as a linker that is connecting each cluster consisting of the corresponding metal cation and the TC ligand in each infinite chain. While the frameworks of compounds 1 , 2 , 3 , and 5 are thermally robust up to ca. 300 ºC, that of compound 4 reveals thermal stability to ca. 250 ºC. The observed band gaps of the title compounds range from 1.94 to 3.64 eV. Photoluminescence (PL) properties arising from the intraligand as well as the ligand‐to‐metal charge transfer were studied for compounds 1 and 4 . The magnetic behavior of compound 2 is described by a coupled linear trimer, while those of compounds 3 and 5 are turned out to be coupled spin dimers.

    更新日期:2020-01-02
  • Activation of Water at Active‐site Cavity of Zinc Phthalocyanine with Tris(pentafluorophenyl)borane
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2020-01-01
    Takuro Ikeuchi; Ryota Kudo; Tatsuya Yoshii; Nagao Kobayashi; Yu Kitazawa; Mutsumi Kimura

    Activation of water bound with Zn2+ has attracted much attention as an artificial model of natural enzymes. Despite many attempts, water activation accompanied with a change in the coordination geometry of Zn2+ in complexes remains a challenge. In this study, we discover a new structure that is composed of partially protonated zinc phthalocyanine (ZnPc), hydroxide ion, and tris(pentafluorophenyl)borane (TPFB). The coordination of TPFB with water bounded with ZnPc results in the dissociation of water, and the dissociated proton from water moves to one nitrogen atom of the phthalocyanine ring through the intramolecular proton transfer. On the bassis of this reaction, the coordination geometry transforms from a five‐coordinated specie to a distorted tetrahedral specie. The Zn2+‐bound hydroxide nucleophile in the ZnPc‐TPFB complex attacks amide of e‐caprolactam to produce hydrolyzed 6‐aminohexanoic acid in toluene.

    更新日期:2020-01-02
  • 更新日期:2019-12-30
  • 更新日期:2019-12-30
  • Synthesis and Structure of the Sodium Phosphidosilicate Na2SiP2
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2019-12-29
    Arthur Haffner; Anna-Katharina Hatz; Constatin Hoch; Bettina V. Lotsch; Dirk Johrendt

    Abstract: Ion conductors of light alkaline metals based on earth‐abundant elements are important components for all‐solid‐state batteries. The new sodium‐rich phosphidosilicate Na 2 SiP 2 was synthesized by solid state reaction of stoichiometric amounts of the elements at 973 K and characterized by single‐crystal X‐ray diffraction (space group Pccn (no. 56), a = 12.7929(5) Å, b = 22.3109(9) Å, c = 6.0522(2) Å and Z = 16) and solid‐state NMR under MAS conditions. The compound exhibits dark‐red merohedral drilling crystals and its crystal structure is constituted of edge‐sharing SiP 4 tetrahedra connected to infinite ∞ 1 [SiP 4/2 ] chains. The sodium ions between the chains are fairly mobile. Electric impedance spectroscopy revealed mixed conduction behavior with electronic and ionic conductivities of σ (e ‐ , 298 K) = 3.5·10 ‐9 Scm ‐1 and σ (Na + , 373 K) = 2.3·10 ‐6 Scm ‐1 with an activation energy of E a = 0.43 eV.

    更新日期:2019-12-30
  • Tetrazine‐Based Metal‐Organic Frameworks as Scaffolds for Post‐Synthetic Modification by Click Reaction
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2019-12-28
    Madhan Vinu; Kulandaivel Sivasankar; Samikannu Prabu; Jeng-Liang Han; Chia-Her Lin; Chun-Chuen Yang; Jan Demel

    Abstract: Metal‐organic frameworks are one of the most active research fields today. Despite the progress in recent years, synthesis of highly porous structures bearing functional groups for specific applications remains a challenge. Here, we describe synthesis of Zr(IV) and Hf(IV)‐based tetrazine containing metal‐organic frameworks, ZrTz‐68 and HfTz‐68 with pore size of 2.1 nm, specific surface area up to 4217 m2 g‐1, and a UiO‐68 topology. The synthesis can be done on a multi‐gram scale from inexpensive linker 4,4’‐(1,2,4,5‐tetrazine‐3,6‐diyl)dibenzoic acid (H2TzDB). oreover, because of the л‐conjugated tetrazine groups these MOFs can be easily post‐synthetically modified by a “click” reaction maintaining the crystallinity of the framework. Due to the diversity of “clickable” substituents, this strategy represents highly versatile tool for a wide range of applications.

    更新日期:2019-12-29
  • Structural differences and redox properties of unsymmetric diiron PDIxCy complexes
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2019-12-28
    Andreas J. Hofmann; Christian Jandl; Corinna R. Hess

    We present two bimetallic iron complexes, [Fe2(PDIeCy)(OTf)4] (1) and [Fe2(PDIpCy)(THF)(OTf)4] (2) coordinated by an unsymmetric ligand. The new ligand, PDIeCy (PDI = pyridyldiimine; e = ethyl; Cy = cyclam), is a variant of the previously reported PDIpCy (p = propyl) ligand, featuring a shorter linker between the two metal coordination sites. The structural and electronic properties of 1 and 2, both in the solid and solution state, were analyzed by means of X‐ray crystallography, and spectroscopic methods, including 19F‐NMR. The two ligand platforms yield markedly different diiron structures: the PDIeCy ligand permits formation of a bridged, μ‐OTf complex, while the two iron centers of the PDIpCy‐based 2 remain unconnected, directly, under all conditions examined. Both compounds contain electronically non‐coupled high‐spin (S = 2) ferrous centers, as established by Mössbauer spectroscopy and magnetic susceptibility studies. Cyclic voltammetry demonstrates the rich redox chemistry of the compounds, involving both ligand and metal‐centered redox processes. Moreover, we synthesized the two‐electron reduced [Fe2(PDIeCy)]2+ form of 1, which contains the dianionic PDI2‐ ligand, and represents a two‐electron charge localized complex.

    更新日期:2019-12-29
  • Palladium Complexes of Thio/Seleno‐Ether Containing N‐HeterocyclicCarbenes: Efficient and Reusable Catalyst for Regioselective C‐H Bond  Arylation
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2019-12-28
    Ramprasad Bhatt; Nattamai Nattamai Bhuvanesh; Kamal Nayan Sharma; Hemant Joshi

    The synthesis of the novel S,CNHC type half‐pincer ligand precursors (L1 and L2) is described herein by using the atom economy reactions of 1‐(2‐(phenylthio)ethyl)‐1H‐imidazole with benzyl bromide and bromodiphenylmethane, respectively. The analogous reaction of 1‐(2‐(phenylselanyl)ethyl)‐1H‐imidazole with 2‐bromoethyl phenyl sulfide has also resulted in a imidazolium bromide (L3) which is a precursor of novel S,CNHC,Se type pincer ligand. The route of silver‐NHC transmetalation was employed to get the palladium complexes [Pd(L1/L2−HBr)Cl2] (C1 and C2) and [Pd(L3−HBr)Cl]BF4 (C3). Thermally, robust and moisture/air insensitive palladium complexes C1‐C3 have been explored in the catalysis of C‐H bond arylation of imidazoles. The protocol operates under mild reaction conditions in open air with an excellent regioselective C‐H bond arylation at C‐5 position in imidazoles. All the complexes were found to be efficient (yield up to 97% in 12 h) in the catalysis, however, the activating pincer ligand framework containing Pd catalyst C3, was found to be utmost effective among the three catalysts. Only 0.5 mol% catalyst loading is required to achieve admirable yield of the desired cross‐coupled products. More importantly, the catalyst C3 has also been found recyclable up to five cycles with minor decrease in efficiency which is highly desirable feature for the development of economical and sustainable industrial reaction processes.

    更新日期:2019-12-29
  • Highly Efficiency and Uncommon Photoluminescence Behaviors Combined with Multiple Dielectric Responses in Manganese(II) Based Hybrid Phase Transition Compounds
    Eur. J. Inorg. Chem. (IF 2.578) Pub Date : 2019-12-27
    Ya-Xing Wu; Chang-Feng Wang; Hui- Hui Li; Fan Jiang; Chao Shi; Heng-Yun Ye; Yi Zhang

    A series of multifunctional photoluminescent materials, [pyrrolidinium] 2 MnBr 4 ( 1 ), [ N ‐methylpyrrolidinium] 2 MnBr 4 ( 2 ) and [ N ‐methylpyrrolidinium]MnBr 3 ( 3 ) were obtained by means of regulating diversely organic cations and different coordination modes of inorganic metal ions. Interestingly, compounds 1 , 2 and 3 exhibit different dielectric switch and relaxation behaviours in the process of structural transformations. Furthermore, compounds 1 , 2 and 3 possess intriguing photoluminescence properties. When subjected to UV light, tetrahedrally coordinated compound 1 shows extraordinarily strong green light emission with a high quantum yield of 51.41%. By changing the organic cation, tetrahedrally coordinated 2 exhibits an unusual orange emission under ultraviolet excitation, which is different from the conventional tetrahedrally coordinated manganese‐based compounds. By the regulation of coordination modes of inorganic metal ions, octahedrally coordinated compound 3 emits bright red emission with a high quantum yield of 36.76 %. This finding may open a new approach toward designing multifunctional photoluminescent materials.

    更新日期:2019-12-29
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