Skeleton Vibrations and Force Constants of ［Fe_2Cr（μ_3－O）（glycine）_6（H_2O）_3］（NO_3）_7．3H_2O

ＳｋｅｌｅｔｏｎＶｉｂｒａｔｉｏｎｓａｎｄＦｏｒｃｅＣｏｎｓｔａｎｔｓｏｆ［Ｆｅ_２Ｃｒ（μ_３－Ｏ）（ｇｌｙｃｉｎｅ）_６（Ｈ_２Ｏ）_３］（ＮＯ_３）_７．３Ｈ_２ＯＺｈａｎｇＬｉｎ－Ｎａ，ＬｉｎＺｈｅｎｇ－Ｙａｎ（ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙｏ...     

对称三唑Schiff碱与铜的配合物合成及性能

合成了４种新型对称三唑水杨醛Ｓｃｈｉｆ碱的铜配合物［ＣｕＬ１Ｃｌ２］（Ⅰ）和三核配合物［Ｃｕ３（Ｌ２－Ｌ４）２Ｃｌ４］·ｎＨ２Ｏ（Ⅱ～Ⅳ），其中Ｌ１，Ｌ２，Ｌ３和Ｌ４分别为４－氨基－１，２，４－三唑、４－氨基－３，５－二甲基－１，２，４－三唑、４－氨基－３，５－二乙基－１，２，４－三唑和４－氨基－３，５－二羟甲基－１，２，４－三唑的水杨醛Ｓｃｈｉｆｆ碱．经元素分析、电导、红外光谱、热重分析、电子光谱、ＥＳＲ和变温磁化率表征，该类配合物为畸变四方构型．配合物Ⅱ的变温磁化率表明，铜离子间存在弱的反铁磁相互作用，Ｊ＝－１８．９ｃｍ－１，ｇ＝２．０８，Ｆ＝２．７×１０－３．配合物对Ｂ细胞增殖有抑制作用．     

N，N＇－二（2－羟基苄烯）－2－羟基苯甲基二胺及N，N＇－二（2－羟基苄基）－2－羟基苯甲基二胺与过渡金属配合物的合成和表征

在四氢呋喃中合成了Ｓｃｈｉｆｆ碱配体Ｎ，Ｎ＇－二（２－羟基苄烯）－２－羟基苯甲基二胺（ＳＢ）与二价过渡金属镍、铜、锌的三核或双核配合物；用钠汞齐还原ＳＢ得到了其氢化物Ｎ，Ｎ＇－二（２－羟基苄基）－２－羟基苯甲基二胺（ＨＳＢ），并在乙醇中合成了它与铜的双核配合物。对这些配合物进行了元素分析和热分析，并测定了电导、红外光谱和紫外光谱，确定了分子式，讨论了可能的配位结构。     

基于三核镉的二维金属有机骨架[Cd_3(L)_2(cis-1,4-chdc)_2(trans-1,4-chdc)]的合成、结构和表征(英文)

The title metal-organic framework, [Cd3(L)2(cis-1,4-chdc)2(trans-1,4-chdc)] (1, L=2-(4-fluorophenyl)-1H-imidazo [4,5-f][1,10]phenanthroline, 1,4-H2chdc=1,4-cyclohexanedicarboxylic acid) has been synthesized under hydrothermal condition and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a=0.851 71(17) nm, b=1.199 9(2) nm, c=1.521 4(3) nm, α=68.13(3)°, β=79.48(3)°, γ=82.32(3)°, V=1.415 0(5) nm3, Z=1, C62H52Cd3F2N8O12, Mr=1 476.32, Dc=1.732 g·cm-3, F(000)=738, μ(Mo Kα)=1.197 mm-1, R=0.067 6 and wR=0.135 4. The cis-1,4-chdc2- ligands bridge the Cd(Ⅱ) cations to form a trinuclear Cd(Ⅱ) based double chain along the a axis. Further, the trans-chdc2- ligands link the adjacent double chains to yield an interesting two-dimensional network. The L ligands are attached on both sides of the layers.     

Magnetic properties of linear trimers in fluoride analogs of tetragonal tungsten bronze

The compounds KZnTiF₆, KZnVF₆, KVScF₆, KCrScF₆, and KMnScF₆ are fluoride analogs of Tetragonal Tungsten Bronze. M²⁺-M³⁺ ionic ordering in these fluorides provided systems which contained linear trinuclear complexes of their respective paramagnetic ions. Magnetic coupling within these linear trimers occurred below 100 K in each of the five systems. Derived magnetic susceptibility equations were fitted to observed magnetic susceptibilities for each of the possible spin systems: KZnTiF₆ (S=1/2), J/k=−114 K; KZnVF₆ (S=1), J/k=−39 K; KVScF₆ (S=3/2), J/k=−16 K; KCrScF₆ (S=2), J/k=−4 K; and KMnScF₆ (S=5/2), J/k=−7.5 K.     

Relaxation effects in the Mössbauer spectra of iron complexes with fatty acids

Six new oxo trinuclear iron(III) complexes of the type [Fe₃O(R–COO)₆(H₂O)₃] X, where X= or Cl^– and R=C₅, C₇, C₈, C₉ were synthesized and investigated by Infra Red, Mössbauer Spectroscopy and magnetic measurements. The data pointed to a high spin state (S=5/2) for iron and for antiferromagnetic interactions. The asymmetrical shape of the Mössbauer doublet and its temperature dependence was treated using the Blume relaxation model. The relaxation process is influenced by both X and R components.     

Preparation and reactivity of metal-containing monomers

Thermal transformations (at 340 to 390 °C) of coprecipitates of iron and cobalt acrylates, [Fe₃O(CH₂CHCOO)₆OH][Co(CH₂CHCOO)₂]_2.4 (1) and [Fe₃O(CH₂CHCOO)₆OH][Co(CH₂CHCOO)₂]_1.5·3H₂O (2), are studied. The dependence of the degree of gas evolution () on time is described by the equation () wherek ₁=2.3 · 10¹² · exp[–49500/(RT)] s^–1,k ₂=6.0 · 10⁶ · exp[–33000/(RT)] s^–1 andk ₁=2.6 · 10¹² · exp[–49000/(RT)] s^–1,k ₂=6.6 · 10⁵ · exp[–30000/(RT)] s^–1 for cocrystallizates1 and2, respectively. The coefficient ₁ decreases as the temperature increases. The value of ₁ for compound1 is higher than that for compound2. The composition of products of the transformations of1 and2 are studied. The main solid state products of the decomposition are nanometer-sized particles of cobalt ferrite, CoFe₂O₄, with a narrow size distribution stabilized by the polymeric matrix. The thermal transformations of cocrystallizates1 and2 include dehydration, thermal decomposition, copolymerization in the solid state, and decarboxylation of the metallocarboxylate groups of the polymer. The effect of the ratio between the Fe clusters and the Co-containing fragments on the process of thermal transformation is analyzed.For Part 40, seeRuss. Chem. Bull., 1994,43, 2020.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 885–893, May, 1995.The authors are grateful to A. N. Titkov for optical microscopic and electron microscopic studies.     

Synthesis,Crystal Structure and Fluorescent Property of [Ag_3(μ_3-I)_2(μ_2-dppm)_3]I·0.5THF·0.5H_2O

1INTRODUCTIONThepropensityforaggregationofformallyclosed-shelld10metalionsinpolynuclearcoordinationcom-plexesandsolid-statelatticeshaslongbeenrecog-nizedandexplored.Simultaneouslythesupramole-cularassemblyanddesignofmoleculeswithrichphotophysicalpropertieshavearousedgreatinter-est[1～4].Sincebis(diphenylphino)methane(dppm)ligandiswidelyusedfortheformationofpoly-nuclearmetalcomplexeswithmosttransitionmetalions[5～7],weutilizeddppmasabridgingligandtoreactwithsilveriodide,resultinginabicapped…     

Thermal decomposition of some linear trinuclear schiff base complexes with acetate bridges

Ni(II)–M(II)–Ni(II) nuclear structured complexes were prepared from N,N’-bis(salicylidene)-1,3-propanediamine (LH2) and its derivatives N,N’-bis(salicylidene)-2,2’-dimethyl-1,3-propanediamine (LDMH₂) and N,N’-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH3), where M represents one of the following metal ions; Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). Two different μ-bridges are found between the metal nucleus of the complexes. The phenolic oxygens and acetate ions tend to form μ-bridges between the terminal Ni(II) ions and central metal(II) ion. The coordinatively bonded DMF molecules, in the complexes, were observed to abandon the structure between 160–180°C. Further heating resulted primarily in the thermal decomposition of the complexes above 310°C, whereas metal oxide residue mixtures were observed above 650°C.     

Robust Triplatinum Redox-Chromophore for a Post-Synthetic Color-Tunable Electrochromic System

An electrochromic system showing ease of color tunability has been constructed using a triple-decker Pt^II complex [Pt₃(μ₃-pydt)₂(bpy)₃]²⁺ (H₂pydt=2,6-pyridinedithiol, bpy=2,2′-bipyridine). The divalent complex undergoes electrochemically quasi-reversible two-electron transfer coupled with the coordination/dissociation of axial ligands, forming higher valent Pt(+2.67) species [Pt₃X₂(μ₃-pydt)₂(bpy)₃]²⁺ (X=Cl⁻, Br⁻, and SCN⁻). These higher valent species exhibit characteristic colors ranging from red to cyan depending on the counter anion X⁻ of the electrolyte. The triple-decker structure provides a novel multicolor electrochromic system with favorable stability and reversibility. Theoretical calculations indicate that the colors of the Pt(+2.67) species are tunable by the trans influence of the axial ligand X⁻. This novel strategy of post-synthetic color-tuning using triplatinum systems should enable the facile preparation of colorful electrochromic devices without any complicated procedures, which may find application in flexible displays, optical devices, and sensors.