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1.
A. S. Rozenberg E. I. Aleksandrova G. I. Dzhardimalieva A. N. Titkov A. D. Pomogailo 《Russian Chemical Bulletin》1993,42(10):1666-1672
The thermal decomposition of iron (III) acrylate, [Fe3O(CH2=CHCOO)6 · 3H2O]OH (FeAcr), a monomer with a complex cluster cation, has been studied at 200–370 °C. Thermal transformations of FeAcr occur
in two temperature regions. The rates of gas evolution in the low temperature region (200–300 °C) and the high temperature
region (300–370 °C) are described by first-order equations withk=4.2 · 1021exp[−59000/(RT)] s−1 andk=1.3 · 106exp[−30500/(RT)] s−1, respectively. A study of the qualitative and quantitative composition of the products of FeAcr thermolysis was carried out.
The thermal transformation of FeAcr is a complex process of dehydration, degradation, and polymerization in the solid phase
followed by decarboxylation of the metal-carboxyl groups of the polymer.
for part 33 see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1743–1750, October, 1993. 相似文献
2.
Ruojie Tao Shuangquan Zang Chongzhen Mei Qinglun Wang Benyong Lou Jingyang Niu Yanxiang Cheng Daizheng Liao 《Journal of Cluster Science》2003,14(4):459-469
Two heterometallic trinuclear complexes {[Cu(oxbp)]2Co(H2O)2}1.5DMF0.5H2O (complex 1) and {[Cu(oxbm)]2Co(H2O)2}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]– and [Cu(oxbm)]–[H3oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H3oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm–1 for complex 1 and 2, respectively. 相似文献
3.
Masahiro Mikuriya Yuko Naka Ayumi Inaoka Mika Okayama Daisuke Yoshioka Hiroshi Sakiyama Makoto Handa Motohiro Tsuboi 《Molecules (Basel, Switzerland)》2022,27(13)
A mixed-valent trinuclear complex with 1,3-bis(5-chlorosalicylideneamino)-2-propanol (H3clsalpr) was synthesized, and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The molecule is a trinuclear CoIII-CoII-CoIII complex with octahedral geometries, having a tetradentate chelate of the Schiff-base ligand, bridging acetate, monodentate acetate coordination to each terminal Co3+ ion and four bridging phenoxido-oxygen of two Schiff-base ligands, and two bridging acetate-oxygen atoms for the central Co2+ ion. The electronic spectral feature is consistent with the mixed valent CoIII-CoII-CoIII. Variable-temperature magnetic susceptibility data could be analyzed by consideration of the axial distortion of the central Co2+ ion with the parameters Δ = –254 cm−1, λ = –58 cm−1, κ = 0.93, tip = 0.00436 cm3 mol−1, θ = –0.469 K, gz = 6.90, and gx = 2.64, in accordance with a large anisotropy. The cyclic voltammogram showed an irreversible reduction wave at approximately −1.2 V·vs. Fc/Fc+, assignable to the reduction of the terminal Co3+ ions. 相似文献
4.
The title linear trinuclear complexes, [Fe3L2(CH3COO)2](L=bis-(salicylidene)-1,3-diaminopropane (salpd) (1) and L=bis-(salicylidene)-1,4-diaminobutane (salbd) (2) were synthesized simply using solvothermal method in methanol and were characterized by X-ray single crystal diffraction. [Fe3L2(CH3COO)2](1) was obtained using salicylaldehyde, 1,3-diaminopropane and Fe(CH3COO)2·4H2O via the above method with monoclinic crystal system and space group of P21/c, and lattice parameters of a=0.945 0(8) nm, b=1.037 0(8) nm, c=1.830 5(14) nm, β=94.357(16)°. The [Fe3L2(CH3COO)2](2) was obtained using1,4-diaminobutane instead of 1,3-diaminopropane while keeping the other conditions the same as that for synthesis of [Fe3L2(CH3COO)2] (1). The [Fe3L2(CH3COO)2](2) was in monoclinic crystal system and space group of P21/c, and lattice parameters of a=0.919 0(5) nm, b=1.675 6(9) nm, c=1.270 0(7) nm, β=95.126(11)°. CCDC: 754930, 1; 754931, 2. 相似文献
5.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(3):256-262
Using polynuclear metal clusters as nodes, many high‐symmetry high‐connectivity nets, like 8‐connnected bcu and 12‐connected fcu , have been attained in metal–organic frameworks (MOFs). However, construction of low‐symmetry high‐connected MOFs with a novel topology still remains a big challenge. For example, a uninodal 8‐connected lsz network, observed in inorganic ZrSiO4, has not been topologically identified in MOFs. Using 2,2′‐difluorobiphenyl‐4,4′‐dicarboxylic acid (H2L) as a new linker and 1,2,4‐triazole (Htrz) as a coligand, a novel three‐dimensional CdII–MOF, namely poly[tetrakis(μ4‐2,2′‐difluorobiphenyl‐4,4′‐dicarboxylato‐κ5O1,O1′:O1′:O4:O4′)tetrakis(N,N‐dimethylformamide‐κO)tetrakis(μ3‐1,2,4‐triazolato‐κ3N1:N2:N4)hexacadmium(II)], [Cd6(C14H6F2O4)4(C2H2N3)4(C3H7NO)4]n, (I), has been prepared. Single‐crystal structure analysis indicates that six different CdII ions co‐exist in (I) and each CdII ion displays a distorted [CdO4N2] octahedral geometry with four equatorial O atoms and two axial N atoms. Three CdII ions are connected by four carboxylate groups and four trz− ligands to form a linear trinuclear [Cd3(COO)4(trz)4] cluster, as do the other three CdII ions. Two Cd3 clusters are linked by trz− ligands in a μ1,2,4‐bridging mode to produce a two‐dimensional CdII–triazolate layer with (6,3) topology in the ab plane. These two‐dimensional layers are further pillared by the L2− ligands along the c axis to generate a complicated three‐dimensional framework. Topologically, regarding the Cd3 cluster as an 8‐connected node, the whole architecture of (I) is a uninodal 8‐connected lsz framework with the Schläfli symbol (422·66). Complex (I) was further characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, thermogravimetric analysis and a photoluminescence study. MOF (I) has a high thermal and water stability. 相似文献
6.
The localized molecular orbitals and their energy levels for the clusters [Fe3S4(SH)3]2–, [(HS)3Fe3S4·Ni(PH3)]2–, [Mo3S4(OH2)9]4+, and [Mo3S4·Ni]4+ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe3S4]+ and [Mo3S4]4+ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M
3(3-S)(-S)3} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M3S3} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo3S4]4+ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe3S4]+ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo3S4]4+ cluster. 相似文献
7.
Jianfeng Zhang Dr. Marco Wenzel Johannes Steup Gerrit Schaper Dr. Felix Hennersdorf Prof. Dr. Hao Du Prof. Dr. Shili Zheng Prof. Dr. Leonard F. Lindoy Prof. Dr. Jan J. Weigand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(1):e202103640
Effective receptors for the separation of Li+ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4-phosphoryl pyrazolones, H L 2-H L 4, in the presence of the typical industrial organophosphorus co-ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li+ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co-ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid-liquid extraction in the presence of TOPO revealed an unprecedented high Li+ extraction efficiency (78 %) for H L 4 compared to the use of the industrially employed acylpyrazolone H L 1 (15 %) and benzoyl-1,1,1-trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li+ over Na+, K+ and Cs+ under mild conditions (pH ∼8.2) confirms that H L 2-H L 4 represent a new class of ligands that are very effective extractants for use in lithium separation. 相似文献
8.
9.
用密度泛函理论结合对称性破损方法(DFF-BS)研究了混合桥联三核镍配合物的磁交换耦合作用.这类化合物是由三唑和异硫氰酸根桥联形成的混合桥配合物.计算表明,在标题化合物中,三唑桥传递反铁磁耦合作用,而异硫氰酸根桥传递铁磁耦合作用;并且,随着异硫氰酸根取代三唑桥的数目增加,配合物的铁磁作用增强,在一定意义上说明了混合桥磁耦合作用的加合性.Mulliken自旋布居分析表明,无论是三唑桥还是异硫氰酸根桥,它们的磁交换作用机理都是磁中心的自旋离域.分子磁轨道分析显示,对于三唑桥,在局域磁轨道之间存在着强的轨道作用,导致了反铁磁耦合;对于异硫氰酸根桥,局域磁轨道之间弱的相互作用,表现了铁磁耦合作用.对标题化合物的研究说明了DFF-BS方法可用于三核体系磁交换作用的研究. 相似文献
10.
A novel trinuclear nickel(Ⅱ) complex [Ni3(bushz)2(Himdz)2(H2O)2]?2DMF (1, bushz=N-butylsalicylhydrazide, Himdz=imidazole, DMF=N,N-dimethyl-formamide) has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P21/c with a=7.706(7), b=14.882(6), c=18.639(6) , β=108.08(2)o, V=2032(1) 3, Dc=1.525 g/cm3, Mr=932.95, Z=2, F(000)=972, μ=1.442 mm-1, the final R=0.0359 and wR=0.0771. The three nickel(Ⅱ) atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3+/Ni2+ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied. 相似文献