簇离子Mo_3S_4M~（n＋）中M与Mo成键作用及电子光谱（M＝Fe、Ni，n＝4；M＝Cu，n＝5）

应用ＩＮＤＯ／Ｓ半经验量子化学方法，对簇合物离子Ｍｏ３Ｓ和Ｍｏ３Ｓ４Ｍｎ＋（Ｍ＝Ｆｅ、Ｎｉ，ｎ＝４；Ｍ＝Ｃｕ，ｎ＝５）分别进行分子轨道计算。根据计算得到的簇离子中的原子表观电荷和成键指标，说明Ｆｅ、Ｎｉ、Ｃｕ＋与Ｍｏ３Ｓ成键作用的相对强度依次是Ｆｅ－Ｍｏ＞Ｎｉ－Ｍｏ＞Ｃｕ＋－Ｍｏ。比较了用含组态作用的ＩＮＤＯ／Ｓ方法计算得到的电子跃迁能与实验得到的电子吸收光谱值，并讨论了吸收峰归属情况。对于Ｍ为Ｆｅ、Ｎｉ的簇离子Ｍｏ３Ｓ４Ｍ４＋，最低能量的电子跃迁吸收峰起源于异金属间电荷转移跃迁（ＭＭ’ＣＴ）；而Ｍｏ３Ｓ４Ｃｕ（５＋）簇离子观察到的吸收峰主要是Ｍｏ３Ｓ芯的局域内电荷转移跃迁。根据理论计算结果，由Ｃｕ＋离子到Ｍｏ３Ｓ的电荷转移跃迁谱线，大约在４６０００ｃｍ－１以上才能观察到吸收峰。从Ｍｏ３Ｓ４Ｆｅ４＋次低能量吸收峰的实验值１６６００ｃｍ－１和理论值１６５００ｃｍ－１与Ｍｏ３Ｓ的最低能量吸收峰的实验值１６６００ｃｍ－１和理论值１６９００ｃｍ－１比较，表明无论从理论上或实验上都能证实簇离子Ｍｏ３Ｓ４Ｆｅ４＋在能量为１６６００ｃｍ－１处的吸收峰是起因于Ｍｏ３Ｓ芯的局域内电荷转移跃迁。     

Synthesis and structure of a novel MoFe_4S_4 cubane-like cluster (Me_3PhCH_2N)_2[MoFe_4S_4(SC_6H_(11))_7]

Ｉｔｉｓｗｅｌｌｋｎｏｗｎｔｈａｔｉｎｎａｔｕｒｅｔｈｅａｃｔｉｖａｔｉｏｎａｎｄｒｅｄｕｃｔｉｏｎｏｆｄｉｎｉｔｒｏｇｅｎｉｎａｉｒｔｏａｍｍｏｎｉａａｒｅｃａｔａｌｙｚｅｄｂｙｎｉｔｒｏｇｅｎａｓｅａｔａｍｂｉｅｎｔｔｅｍｐｅｒａｔｕｒｅａｎｄｐｒｅｓｓｕｒｅ.ＴｈｅｍａｉｎｃｏｍｐｏｎｅｎｔｓｏｆｔｈｅａｃｔｉｖｅｃｌｕｓｔｅｒｏｆＭｏＦｅｐｒｏｔｅｉｎｉｎｎｉｔｒｏｇｅｎａｓｅａｒｅＭｃｌｕｓｔｅｒ(ＭｏＦｅ7Ｓ9ｃｌｕｓｔｅｒ)ａｎｄＰｃｌｕｓｔｅｒ(Ｆｅ8Ｓ8ｃｌｕｓｔｅｒ)[1].Ｉｎｔｈｅｌ…     

ATP与Fe4S4*络合的31P-NMR研究

MgATP结合在铁蛋白的什么部位?众说纷芸,尚无定论。大多数研究者认为,MgATP不是与铁蛋白的活性中心Fe_4S_4原子簇络合,而是与它的非铁部位例如巯基或者外围组织络合。在上述作用模式中,ATP与铁蛋白键合的性质是不确定的。曾主张MgATP与铁蛋白的非铁部位结合的Mortenson等后来用~(31)P-NMR观察到,MgATP与还原态铁蛋白的结合,引起ATP的α-、β-和γ-~(31)P谱峰分别往低磁场漂移8.7、9和7.7ppm,这时他开始认为,这种变化可能是由于ATP与铁蛋白的某部位或者是与其活性中心Fe_4S_4原子簇的络合引起的。铁蛋白的活性中心与其模型化合物在化学性质上是基本相似的。通过化学模拟体系的~(31)P-NMR研究,有助于确定铁蛋白与MgATP的络合方式。     

A 3D Luminescent Metal‐organic Framework Constructed from Cu4I4 Cubane Clusters and Triangular Imidazole Ligand

Abstract . The solvothermal reaction between cuprous iodide and the rigid triangular imidazole ligand in mixed N,N′‐dimethylacetamide (DMA)‐acetonitrile solvent leads to the isolation of the 3D metal‐organic framework [(Cu₄I₄)₃(TIPA)₄] · 7DMA ( 1 ) [TIPA = tri(4‐imidazolylphenyl) amine], which was characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Topologically, the structure of 1 is an unprecedented 3,3,4,4‐connected net with a point symbol of {4.8.10}₂{4.8²}₂{4².8².10²}₂{8⁴.12²}. Compound 1 exhibits orange‐red photoluminescence with an emission maximum at 622 nm at room temperature.     

四核钼簇合物的配体取代反应及产物Mo_4S_4(μ-OAc)_2(dtp)_4的晶体结构

标题化合物(Ⅰ)经由Mo_4S_4(μ-dtp)_4(Ⅱ)[dtp=S_2P(OEt)_2]和Ni(OAc)_2反应而得。(Ⅰ)晶体属单斜晶系,空间群P2/c,a=13.176(4),b=11.699(3),c=18.526(4)(?),β=116.11(3)°,V=2564(3)(?)~3,Z=2,D_c=1.776g·cm~(-3)。晶体结构由直接法解出,最终偏离因子R=0.085。本文结果表明,可由已知的四核钼簇合物经过配体置换反应,合成得到其簇骼中心[Mo_4S_4]保持不变并具有-OAc作为桥式配体和-dtp作为端基配体的混合配体类立方烷[Mo_4S_4]簇合物。     

C4Sm-4相对稳定性的从头算研究

从五十年代至今，对用通式C；；0：－…＝3，45，6n表征的氧碳化合物（OXOCCbollS）已进行了大显的理论和实验研究，认为它们是一类新的芳香化合物山．用硫、硒等取代氧的类似化合物（一般称为类氧碳化合物或假氧碳化合物，ps。11。10－OX。。CCI．b0118）的研究也有许多报导［     

系列Fe4S4簇合物的光谱分析

本文报道了自合成的4种类立方烷型Fe_4S_4簇合物[Et_4N][Fe_4S_4(Et_2dtc)_4]、[Et_4N]_2·[Fe_4S_4(Et_2dtc)_4]、[Et_4N]_3[Fe_4S_4(Et_2dtc)_4]、[Bu_4N]_2[Fe_4S_4(PhS)_4]的UV-Vis和IR光谱数据,对照X光衍射测定结果,依据配体场弱场理论,对各光谱进行了分析和指认。讨论了配离子构型、中心离子氧化态对d-d带和荷迁移带的影响及键长、配位环境等几何因素与振动带的关系。     

Synthesis and structure of a novel MoFe4S4 cubane-like cluster (Me3PhCH2N)2 [MoFe4S4 (SC6H11)7]

A novel (Me₃PhCH₂N)₂[MoFe₄S₄(SC₆H₁₁)₇] cubane-like cluster was obtained from a reaction system including (NH₄)₂MoS₄, FeCl₂ and NaSC₆H₁₁ in methanol, and characterized by X-ray crystallography. The title compound crystallizes in triclinic space group witha = 1.523 1(3), b =1.610 5(3),c = 1.838 3(4) nm, α = 77.18 (3)°, β = 75.17(3)°, γ = 64.60(3)°, and Z = 2. Also included in this paper are the discussions on the variation of the reaction products obtained from the participation of cyclohexylthiolate and on the changes of the structural features of the products. Project supported by the National Natural Science Foundation of China and the Climbing Program—State Key Project for Fundamental Research in China, and Hong Kong Research Grants Council (Earmarked Grant No. CUHK. 311/94p).     

Investigation of Spectra（NMR,Mass）of Some Fe3S3Cluster Compounds

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｉｒｏｎ ｓｕｌｆｕｒｐｒｏｔｅｉｎｉｓｏｎｅｏｆｔｈｅｍｅｔａｌｐｒｏｔｅｉｎｓｔｈａｔｃａｎｔｒａｎｓｍｉｔｅｌｅｃｔｒｏｎｓ.Ｉｒｏｎ ｓｕｌｆｕｒｐｒｏｔｅｉｎｓａｒｅｆｏｕｎｄｉｎｍｏｓｔｏｆｔｈｅｌｉｆｅｆｏｒｍｓ,ｙｅｔｉｔｗａｓｎｏｔｕｎｔｉｌａｒｏｕｎｄ1960ｔｈａｔｉｒｏｎ ｓｕｌｆｕｒｐｒｏｔｅｉｎｓｗｅｒｅｆｏｕｎｄｉｎｐｈｏｔｏｓｙｎｔｈｅｔｉｃｏｒｇａｎｉｓｍ〔1〕,ｎｉｔｒｏｇｅｎ ｆｉｘ ｉｎｇｂａｃｔｅｒｉａ〔2〕,ａｎｄｓｕｂｍｉｔｏｃｈｏ…     

Syntheses and structural characterizations of Fe_4S_4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.     

Crystal Structure of Complex （Et4N）[VFe3S4Cl3（CH3CN）3]

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅ1980,ｍａｎｙＶ/Ｆｅ/Ｓｈｅｔｅｒｏｍｅｔａｌｌｉｃｓｕｌｆｕｒｃｌｕｓｔｅｒｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄ.ＲａｕｃｈｆｕｓｓｅｔａｌｏｂｔａｉｎｅｄｔｗｏｋｉｎｄｓｏｆＶ/Ｆｅ/Ｓｃｏｍｐｏｕｎｄｓ[1]ｕｓｉｎｇ(ＣＨ3Ｃ5Ｈ4)2Ｖ2Ｓ4ａｓａｎｏｒｇａｎｏｍｅｔａｌｌｉｃｌｉｇａｎｄ,ｏｎｅｉｓ(ＭｅＣｐ)2Ｖ2Ｆｅ2(ＮＯ)2Ｓ4ｗｉｔｈａｃｕｂａｎｅｌｉｋｅｓｔｒｕｃｔｕｒｅａｎｄａｎｏｔｈｅｒｉｓ(ＭｅＣｐ)2Ｖ2Ｓ4Ｆｅ(ＮＯ)2ａｎｄ(ＭｅＣｐ)2Ｖ2Ｓ4…     

Field-Induced SMM Behaviour of Tetranuclear Coordination Clusters with a Cubane [Ni4O4] Core

Two tetranuclear Ni(II) complexes: [Ni₄(HL¹)₄] ⋅ H₂O ( 1 ) and [Ni₄(HL²)₄] ⋅ 1.5 dmf ( 2 ) where dmf=dimethylformamide, H₃L¹=4-(tert-butyl)-2-(((2-hydroxy-5-nitrophenyl)imino)methyl)-6-(hydroxymethyl)phenol and H₃L²=4-(tert-butyl)-2-(hydroxymethyl)-6-(((2-hydroxyphenyl)-imino)methyl)phenol, have been prepared and characterized by single crystal X-Ray diffraction, elemental analysis and FT-IR spectroscopy. The solid-state structures reveal the formation of highly symmetric and asymmetric [Ni₄O₄] cubane cores in complexes 1 and 2 , respectively. Extensive magnetic studies show that both complexes present ferromagnetic exchange interactions between the Ni(II) ions within the cubane core with g=2.113(3), J₁=−7.89(8) cm⁻¹, J₂=13.3(1) cm⁻¹ and |D|=11.3(4) cm⁻¹ (for 1 ) and g=2.206(4), J₁=1.0(1) cm⁻¹, J₂=7.8(1) cm⁻¹ and |D|=8.7(2) cm⁻¹ (for 2 ). The large anisotropy, high ground spin state (arising from the ferromagnetic coupling) and the good isolation of the clusters provided by the Schiff base ligands, give rise to the first examples of field-induced single-molecule magnets (FI−SMM) in Ni₄O₄ clusters and to the highest energy barrier reported to date in a Ni₄O₄ cluster.     

Mo－Cu－S原子簇化合物［Mo_2Cu_6S_6（SCMe_3）_2（O）_

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

STUDIES ON SYNTHESES OF MoFe_3S_4 CUBANE-LIKE CLUSTER COMPOUNDS

The features of synthetic processes are described on the basis of the studies of the syntheses of MoFe_3S_4 cubane-like cluster compounds either by self-assembly reactions or by the conversion of linear clusters. The redox properties and the structure of ligands as well as the stoichiometry of reactants have obvious effects upon the core oxidation state and the structure of products. It is indicated that the self-assembly reaction may pass through a combination process oflinear cluster intermediates having structural unit (M,M'=Mo) Fe).     

Synthesis and structure of {Mo_3S_7[S_2P(OC_2H_5)_2]_3}{Mo_3S_4[S_2P(OC_2H_5)_2]_4(SCN)} and interaction between their cluster units

Ｔｈｅｔｒｉｍｏｌｙｂｄｅｎｕｍｃｌｕｓｔｅｒｓｗｉｔｈｇｅｎｅｒａｌｆｏｒｍｕｌａ[Ｍｏ3(μ3Ｓ)(μＳ)3(μｄｔｐ)(ｄｔｐ)3Ｌ](ｄｔｐ=(Ｓ2Ｐ(ＯＣ2Ｈ5)2)-,Ｌ=Ｈ2Ｏ,ｐｙ,ＳＣ(ＮＨ2)2ｅｔｃ.)[1](ｒｅｆｅｒｒｅｄｔｏａｓＭ1ｔｙｐｅ[2]),ａｎｄ[Ｍｏ3(μ3Ｓ)(μＳ2)3(ｄｔｐ)3]Ｘ(Ｘ=Ｃｌ,Ｉ)[3](ｒｅｆｅｒｒｅｄｔｏａｓＭ2ｔｙｐｅ),ａｒｅｔｗｏｍａｉｎｔｙｐｅｓｏｆｔｒｉｍｏｌｙｂｄｅｎｕｍｃｌｕｓｔｅｒｓｅｖｅｒｉｎｖｅｓｔｉｇａｔｅｄｂｙｏｕｒｒｅｓｅａｒｃｈｇｒｏｕｐ.Ａｓｗｅｈａｖｅａｌｒｅａｄｙ…     

Study on the Magnetic Properties of MoFe_3S_4 Single Cubane－like Clusters Containing R_2dtc Ligands

ＳｔｕｄｙｏｎｔｈｅＭａｇｎｅｔｉｃＰｒｏｐｅｒｔｉｅｓｏｆＭｏＦｅ_３Ｓ_４ＳｉｎｇｌｅＣｕｂａｎｅ－ｌｉｋｅＣｌｕｓｔｅｒｓＣｏｎｔａｉｎｉｎｇＲ_２ｄｔｃＬｉｇａｎｄｓＬＩＵＱｉｕ－Ｔｉａｎ；ＤＥＮＧＹｕ－Ｈｅｎｇ；ＣＨＥＮＣｈａｎｇ－Ｎｅｎｇ（?..     

A New Ionic Trimolybdenum Cluster Compound:〔Mo_3S_7(S_2P(iprO)_2)_3〕〔S_2P(iprO)_2〕

1INTRODUCTIoNInthepastdecades,thechemistryofMo-Sclusterscontaininga[Mo,(p,-S)(p-S,),j corehasbeenstudiedtextensively,andmanysuchkindofcompoundshavebeensynthesized.(1'2'3'4iHowever,fewcompoundscontainingadiscreteclus-tercationhavebeenreported.[5iInthispaper,wereportthesynthesisandstructureofthetitlecompound.Thisisanewexampleoftrimolybdenumclustercontainingadiscreteclustercation.2EXPERIMENTALAllmanipulationwerecarriedoutinair.2.1Synthesis0f[M0,S,(S,P(iprO),),jtS,P(iprO),jAmixture…     

系列类立方烷型Fe4S4簇合物的XPS分析

对7种类立方烷型Fe_4S_4簇合物进行了XPS分析,得到了中心离子Fe的价态,给出了系列Fe_4S_4中骨架硫的结合能,由峰合成结果给出各种S、N的比例与按结构式计算的结果相同。     

Synthesis and structure of cluster compounds containing a novel cluster core {Re4STe3}

Three novel cluster compounds K₄[Re₄STe₃(CN)₁₂]·₄H₂O (I), [{Cu(en)₂}₂Re₄STe₃(CN)₁₂]·₅H₂O (II) and [{Cu(trien)}₂Re₄STe₃(CN)₁₂]·2H₂O (III) (en is ethylenediamine, trien is triethylenetetraamine) containing a new cluster core {Re₄STe₃} have been prepared and structurally characterized. According to single crystal X-ray diffraction data, compound I is ionic and represents the arrangement of ions K⁺ and [Re₄STe₃(CN)₁₂]^4?; compounds II and III are molecular and formed by two cationic moieties {Cu(en)₂}²⁺ and {Cu(trien)}²⁺, respectively, coordinated to one cluster anion. In the solid state, S atom positions in the tetrahedron Q₄ (Q = S, Te) are disordered for all three compounds: in I and III sulfur atoms are split over all four Q positions, while in II over two positions.     

3—磺基—4—羟基香豆素希土化合物的合成及性质

在不同条件下制得三种类型的希土与3-磺基-4-羟基香豆素(H_2SHC)化合物,元素分析确定了它们的组成分别为Ln(HSHC)_3·9H_2(Ln=La,Pr,Nd,Gd,Dy,Er,Yb,Y),Ln_2(SHC)_3.nH_2O(Ln:La,Pr,Nd,Sm,Gd,N:4或6)和Na,Ln(3HC),·H:O(Ln:Er,Yb).并通过它们的摩尔电导戌\重,溶解度,红外光谱和电子吸收光谱对各种化合物进行了结构和性质的研究。