新型层状异金属配位聚合物{[(CuL)2Sr(H2O)·Sr2(H2O)7]·2H2O·0.5CH3OH}n的合成、表征及晶体结构

合成了铜锶异金属配位聚合物, 并通过元素分析和IR光谱对其进行了表征, 利用X射线单晶衍射测定了其晶体结构. 该化合物为具有{[(CuL)2Sr(H2O)·Sr2(H2O)7]·2H2O·0.5CH3OH}n化学组成的二维层状配位聚合物[H4L=N-(3-羧基水杨醛)-N'-(2-羟基苯甲酰基)乙撑二胺], 其结构单元由两个相邻的片段组成, 这些结构单元彼此相互配位, 从而形成了一种结构新颖的层状配位聚合物.     

Heterometallation of Photoluminescent Silver(I) Sulfide Nanoclusters Protected by Octahedral Iridium(III) Thiolates

The recently-increasing interest in coinage metal clusters stems from their photophysical properties, which are controlled via heterometallation. Herein, we report homometallic Ag^I₄₆S₁₃ clusters protected by octahedral fac-[Ir(aet)₃] (aet=2-aminoethanethiolate) molecules and their conversion to heterometallic Ag^I₄₃M^I₃S₁₃ (M=Cu, Au) clusters. The reactions of fac-[Ir(aet)₃] with Ag⁺ and penicillamine produced [Ag₄₆S₁₃{Ir(aet)₃}₁₄]²⁰⁺ ([ 1 ]²⁰⁺), where a spherical Ag^I₄₆S₁₃ cluster is covered by fac-[Ir(aet)₃] octahedra through thiolato bridges. [ 1 ]²⁰⁺ was converted to [Ag₄₃M₃S₁₃{Ir(aet)₃}₁₄]²⁰⁺ ([ 1^M ]²⁰⁺) with an Ag^I₄₃M^I₃S₁₃ cluster by treatment with M⁺, retaining its overall structure. [ 1 ]²⁰⁺ was photoluminescent and had an emission band ca. 690 nm that originated from an S-to-Ag charge transfer. While [ 1^Cu ]²⁰⁺ showed an emission band with a slightly higher energy of ca. 650 nm and a lower quantum yield, the emission band for [ 1^Au ]²⁰⁺ shifted to a much higher energy of ca. 590 nm with an enhanced quantum yield.     

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacted readily with a number of ditertiary phosphines under chemical activation with trimethylamine-N-oxide. The solid-state and solution structures of these derivatives have been examined. Six structural types have been characterized crystallographically, including one in which a phenyl group migrates from the ditertiary phosphine ligand to the metal framework. There are many more isomers present in solution, most of which are rapidly inter-converting via hydride migrations.     

[M(dipicH2)(H2O)3], M = Ni,Cu, Zn (dipicH2 = dipicolinic acid) – A combined crystallographic,spectroscopic and computational study

Cationic metal complexes of dipicolinic acid (dipicH₂) are stabilized by [Ce(dipic)₃]²⁻ ions in the three isomorphous crystals [M(dipicH₂)(OH₂)₃][Ce(dipic)₃] · 3H₂O (M = Ni, 1; Cu, 2; Zn, 3). Magnetic dilution provided by the bulky anions leads to well-resolved EPR spectra in polycrystalline samples of 2. The cations have 4+2 coordination, the carbonyl atom of the carboxylic acid groups coordinating weakly from trans positions. In the case of 2 this steric distortion is augmented by Jahn–Teller distortion. All the three structures are satisfactorily modelled by calculations based on density functional theory (DFT). The switch of the Jahn–Teller axis upon deprotonation of the complex, leading to the neutral species Cu(dipic)(H₂O)₃, is also reproduced by DFT. Electronic transition energies as well as the g-tensor component of the d⁹ complex obtained are in good agreement with experiment. However, the calculated hyperfine coupling constants are in error. DFT also fails to satisfactorily account for the electronic transition in the d⁸ ion in 1.     

Mn(III) Hexafluoroacetylacetonate as an Oxidative Agent in the Synthesis of Heterobimetallic <Emphasis Type="Italic">β</Emphasis>-Diketonates

New synthetic approach for the preparation of heterometallic β-diketonates has been developed. Three manganese-containing diketonates, InMn(hfac)₃ (1), CdMn₂(hfac)₆ (2), and Hg₂Mn₂(hfac)₆ (3), have been isolated in quantitative yields by employing the solid state redox reaction of Mn(hfac)₃ with transition and main group metals. The heterometallic molecules are built on Lewis acid–base interactions between diketonate oxygens of the [Mn(hfac)₃]⁻ groups and “naked” metal centers that appear in the form of In⁺, Cd²⁺, and Hg₂²⁺ cations. Compounds 1–3 have been shown to retain a heterometallic structure upon sublimation–deposition procedure as well as in solutions of non-coordinating solvents.     

Solvothermal Synthesis,Crystal Structure,and Luminescent Properties of Three Heterometallic Lanthanide‐Transition‐Metal Frameworks Constructed from Three Types of CuBr Motifs

Three three‐dimensional (3D) heterometallic lanthanide‐transition‐metal (hetero‐Ln‐TM) compounds with the formula [Ln₆(Cu₄Br₃)(Cu₂Br₂)₂(Cu₂Br)(IN)₂₀(H₂O)₁₂] · 2H₂O [Ln = Gd ( 1 ), Ln = Sm ( 2 ), Ln = Eu ( 3 )] based on the linkages of one‐dimensional Ln organic chain and Cu_mBr_n units were synthesized by mixing Ln₂O₃ with isonicotinic acid (HIN = pyridine‐4‐carboxylic acid) under hydrothermal condition. During the synthesis, two ligands were used: the isonicotinate (IN^–) stabilizes the cluster and links the one‐dimensional Ln organic chains and Cu_mBr_n motif, whereas Br^– anions play a very important role in the formation of the distinct Cu_mBr_n units. It is interesting that there are three different Cu‐Br motifs: a closed four‐membered ring [Cu₂Br₂] subunit, a linear [Cu₂Br] subunit, an S‐sharp [Cu₄Br₃] subunit. Strong fluorescence of compounds 2 and 3 suggests an efficient energy transfer from the ligand to Eu³⁺ ions. The luminescent investigation indicates that 2 and 3 are excellent candidates for fluorescent materials.     

Cytotoxic and Antimicrobial Properties of Copper(II) Complexes of Pyridine and Benzimidazole Derivatives

The cytotoxic and antimicrobial activity of a series of six copper(II) complexes with phosphate and hydroxymethyl derivatives of pyridine and benzimidazole were investigated. The complexes and the corresponding free ligands were tested against Staphylococcus aureus ATCC 6538, Staphylococcus epidermidis ATCC 12228, Pseudomonas aeruginosa ATCC 15442, Escherichia coli ATCC 25922, Proteus hauseri ATCC 13315, and Candida albicans ATCC 10231. Among the tested copper(II) complexes, compounds 2 and 5 containing 1H‐benzimidazol‐2‐ylmethyl diethyl phosphate and 2‐(hydroxymethyl)benzimidazole as ligands, respectively, were most active and limited the growth of S. aureus, E. coli, and C. albicans by 30–60 % according to concentration and microorganism. The in vitro cytotoxic activity of the Cu^II complexes and free ligands towards cancerous B16 (murine melanoma) and non‐cancerous 10T1/2 (murine fibroblasts) cell lines was determined. The 10T1/2 cells were treated with the compounds at concentrations equal to IC₅₀ values for B16 cells. In spite of the use of relatively high concentrations of the complexes, the viability of 10T1/2 cells was very high, ca. 80 % in some cases. Stability of the Cu^II complexes was evaluated in water solutions by UV/Vis spectroscopy. The copper(II) complex of 4‐(hydroxymethyl)pyridine was synthesized and identified.     

Stable Heterometallic CuII‐BaII‐2,5‐Thiophenedicarboxylate Framework with High Capacity for Light Hydrocarbons

The heterometallic Cu^II‐Ba^II coordination polymer, namely [CuBa(tdc)₂(H₂O)(DMF)]_n ( 1 ) (H₂tdc = 2,5‐thiophenedicarboxylic acid, DMF = N,N′‐dimethylformamide), was solvothermally synthesized by the reaction of H₂tdc, CuCl₂ · 2H₂O, and Ba(NO₃)₂. Single crystal X‐ray diffraction analysis reveals that compound 1 features a 3D intricate framework with the 1D channels occupied by the coordinated solvent molecules. After removing the coordinated solvent molecules, the desolvated samples of 1a exhibit high capacity for light hydrocarbons.     

Syntheses and Structures of Two Coordination Polymers Containing Macrocyclic Oxamide and Isophthalic Acid Derivatives

Two novel coordination polymers [Cd(NiL)(aipt)](1) and [Mn(nipt)(NiL)₂]稨₂O(2)(NiL, H₂L=2,3-dioxo- 5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H₂aipt=5-aminoisophthalic acid, H₂nipt=5-nitroisoph- thalic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 consist of different 1D chains including both oxamide and 5-aminoisophthalate or 5-nitroisophthalic bridge. And all these chains were further interlinked via hydrogen bonds, resulting in a 2D architecture in compounds 1 and 2.     

3D异金属Bi(Ⅲ)-Pr(Ⅲ)配位聚合物的合成、晶体结构和热稳定性

在水溶液中合成了双金属配位聚合物({[(NO3)(H2O)3Pr(μ4-Hedta)Bi-(NO3)2]·2H2O}2)n, 并通过元素分析、红外光谱和X射线单晶衍射等手段进行了表征. 该配合物为单斜晶系, P2(1)/n空间群, a=1.26831(18) nm, b=0.82189(12) nm, c=2.3755(3) nm, β=105.055(2)°, R=0.0429, V=2.3913(6) nm3, Z=4. Bi(Ⅲ)-Pr(Ⅲ)间通过配阴离子Hedta3-中4个羧基的桥联作用构建配合物的3D结构. TG-DSC结果表明, 该配合物热分解经历脱水、配体分解以及盐分解过程, 残余物为Bi-Pr-O的三元复合氧化物.