[Pt2(P2O4H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d⁸配合物[Pt₂(P₂O₄H₂)₄]^4-和[Pt₂(P₂O₄CH₄)₄]^4-的基态和激发态结构。结果表明基态Pt-Pt距离分别为0.290 5和0.298 7 nm，与实验的0.292 5和0.298 0 nm符合。NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质。CIS计算揭示电子激发到Pt-Pt的σ(p_z)成键轨道使得相互作用增强。保持激发态几何，含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475 nm，与实验值512和510 nm接近。     

双核Au(I)磷硫配合物激发态性质和金属间弱相互作用的从头算研究

采用MP2和CIS方法分别优化双核Au(I)磷硫配合物, [Au₂(SHCH₂SH)₂]^2＋ (1), [Au₂(SHCH₂SH)(PH₂CH₂PH₂)]^2＋(2), [Au₂(PH₂CH₂PH₂)₂]^2＋ (3), [Au₂(SHCH₂SH)(SCH₂S)] (4), [Au₂(PH₂CH₂PH₂)(SCH₂S)] (5)和[Au₂(SCH₂S)₂]^2－ (6), 基态和激发态的结构. 计算结果表明基态时1～6中存在Au(I)-Au(I)弱吸引作用, 激发态时1～5的金属间相互作用明显增强而6则减弱, 这与实验研究结果一致. 单激发组态相互作用计算揭示: 磷硫配体的更替使得Au(I)配合物跃迁性质呈现MC→MMLCT→MLCT的规律性变化(MC: 金属中心; MMLCT: 金属金属到配体电荷转移; MLCT: 金属到配体电荷转移).     

用于痕量监测Zr4+、Cr2O72-、Fe3+、HPO42-和指纹识别的功能化Eu3+/Tb3+配位聚合物荧光探针的构筑

采用芳香族π共轭及含氮原子有机连接剂,合成同构铽、铕发光配位聚合物(CPs){[Eu(PLIA)_1.5(H₂O)₂]·H₂O}_n (1)和{[Tb(PLIA)_1.5(H₂O)₂]·H₂O}_n (2),其中H₂PLIA=5-((吡啶-4-基甲基)氧基)苯-1,3-二甲酸。对合成的配合物进行了结构测定、表征和荧光痕量识别实验研究。2个同构配合物具有理想的三维框架结构,π…π堆积及氢键等弱相互作用增强了其化学稳定性;表征显示配位聚合物1和2具有良好的荧光性质、结晶性、热力学稳定性及结构完整性,可作为荧光传感的材料。1和2对水溶液中的Zr⁴⁺、Cr₂O₇^2-和Fe³⁺、HPO₄^2-具有选择性好、灵敏度高的荧光识别能力,其检出限分别为0.139 μmol·L^-1(1,Zr⁴⁺)、0.626 μmol·L^-1(1,Cr₂O₇^2-)、0.430 μmol·L^-1(2,Fe³⁺)、1.36 μmol·L^-1(2,HPO₄^2-)。探究了1和2作为探针的荧光猝灭机理。更有趣的是,1和2具有指纹识别性能,其荧光指纹纹路清晰连贯,细节明显,可被清晰观察。     

用于痕量监测Zr4+、Cr2O72-、Fe3+、HPO42-和指纹识别的功能化Eu3+/Tb3+配位聚合物荧光探针的构筑

采用芳香族π共轭及含氮原子有机连接剂,合成同构铽、铕发光配位聚合物(CPs){[Eu (PLIA)_1.5(H₂O)₂]·H₂O}_n (1)和{[Tb (PLIA)_1.5(H₂O)₂]·H₂O}_n (2),其中H₂PLIA=5-((吡啶-4-基甲基)氧基)苯-1,3-二甲酸。对合成的配合物进行了结构测定、表征和荧光痕量识别实验研究。2个同构配合物具有理想的三维框架结构,π…π堆积及氢键等弱相互作用增强了其化学稳定性;表征显示配位聚合物1和2具有良好的荧光性质、结晶性、热力学稳定性及结构完整性,可作为荧光传感的材料。1和2对水溶液中的Zr⁴⁺、Cr₂O₇^2-和Fe³⁺、HPO₄^2-具有选择性好、灵敏度高的荧光识别能力,其检出限分别为0.139 μmol·L^-1(1,Zr⁴⁺)、0.626 μmol·L^-1(1,Cr₂O₇^2-)、0.430 μmol·L^-1(2,Fe³⁺)、1.36 μmol·L^-1(2,HPO₄^2-)。探究了1和2作为探针的荧光猝灭机理。更有趣的是,1和2具有指纹识别性能,其荧光指纹纹路清晰连贯,细节明显,可被清晰观察。     

异核Au基电荷转移配合物的结构与Au-Rh配合物取代基效应和激发态的理论研究

采用SVWN、XαVWN和MP2方法优化了Au基电荷转移配合物[Au^ⅠM^Ⅰ(CNH)₂(PH₂CH₂PH₂)₂]²⁺(M=Co(1),Rh (2)和Ir(3))的基态结构。计算表明3种方法都能描述Au-M弱相互作用(Au-M距离在0.268～0.302 nm范围内,伸缩振动频率在99～139     

二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=2,3,4)的合成、结构及体外抗癌活性

丁二酸、戊二酸和己二酸分别与μ-氧-双[三(2-甲基-2-苯基)丙基]锡反应,合成了3个二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂(n=2(1),3(2),4(3))。对化合物1~3进行了元素分析、红外光谱及核磁共振(¹H,¹³C)表征,并通过X-射线晶体衍射分析测定晶体结构。化合物中锡与配基原子构成畸型四面体构型。试验表明,化合物2和3均对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460的增殖具有较强的抑制作用。     

二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=2, 3, 4)的合成、结构及体外抗癌活性

丁二酸、戊二酸和己二酸分别与μ-氧-双[三(2-甲基-2-苯基)丙基]锡反应, 合成了3个二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂(n=2 (1), 3 (2), 4 (3))。对化合物1~3进行了元素分析、红外光谱及核磁共振(¹H, ¹³C)表征, 并通过X-射线晶体衍射分析测定晶体结构。化合物中锡与配基原子构成畸型四面体构型。试验表明, 化合物2和3均对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460的增殖具有较强的抑制作用。     

四种同构镧系金属有机框架的合成、结构和荧光传感Fe3+和盐酸环丙沙星

采用溶剂热法,以含氮四羧酸3,5-二(3′,5′-二羧苯)-1H-1,2,4-三唑(H₄BDT)为配体,成功合成了4种同构镧系金属有机框架(Ln-MOFs)：{[La₃(BDT)₂(HCOO)(H₂O)₅]·0.5H₂O·3DMF}_n (1)、{[Ce₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n (2)、{[Pr₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n (3)和{[Nd₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n (4),并采用单晶X射线衍射、粉末X射线衍射、元素分析、热重、红外、N₂吸附实验和荧光光谱对其进行表征。结果表明,这些Ln-MOFs均为单斜C2/m空间群晶体,是双核为无机建筑单元的三维介孔结构。其中2可选择性荧光检测Fe³⁺离子和盐酸环丙沙星药物分子,检测限分别为4.59和0.77 μmol·L^-1。     

2D层状焦磷酸锰(Ⅱ)[NH4]2[Mn3(P2O7)2(H2O)2]的结构和磁性研究

A two-dimensional layered manganese(Ⅱ) pyrophosphate, [NH₄]₂[Mn₃(P₂O₇)₂(H₂O)₂] (1), has been synthesized hydrothermally. Its structure is determined by single-crystal X-ray diffraction analysis. Its structure is built up by MnO₆ octahedra and P₂O₇ units, with ammonium NH₄⁺ cations residing in the interlayer regions. The manganese pyrophosphate layer consists of infinite chains of cis and trans edge sharing MnO₆ octahedra linked by P₂O₇ units. Magnetic susceptibility measurements show that this compound exhibits ferrimagnetic-like ordering below 3.2 K. Further study shows that there are two possible superexchange pathways via the oxygen anions in Mn²⁺ ions. Owing to the different bridging modes of O^2-, the competition between ferromagnetic interactions and antiferromagnetic interactions in Mn²⁺ ions results in the ferrimagnetic behavior of 1.     

二氰氨根[N(CN)2-]/三氰甲根[C(CN)3-]桥联双核钌RuⅡRuⅢ混合价配合物的设计合成、表征和电子传递行为

trans-[XRu(py)₄(NO)]²⁺(X=Cl，Br)与等物质的量的NaN₃在甲醇中反应后生成中间体trans-[XRu(py)₄(CH₃OH)]⁺，它再与过量的Na[N(CN)₂]或K[C(CN)₃]反应后生成单核配合物trans-XRu(py)₃L(X=Cl，Br，L=N(CN)₂^-，C(CN)₃^-)。单核配合物XRu(py)₄L与[X′Ru(py)₄(CH₃OH)]⁺进行分子组装，生成了一系列双核钌配合物trans-[X(py)₄Ru(μ-L)Ru(py)₄X′]⁺。用等物质的量的NOBF₄或(NH₄)₂[Ce(NO₃)₆]氧化这些Ru^ⅡRu^Ⅱ双核钌配合物，得到了一系列Ru^ⅡRu^Ⅲ混合价配合物trans-[X(py)₄Ru(μ-L)Ru(py)₄X′]²⁺。N(CN)₂-桥联的Ru^ⅡRu^Ⅲ混合价配合物在近红外区存在中等强度的吸收，起源于混合价态间的电荷跃迁(Intervalence Charge Transfer，简称为IVCT)，且其最大吸收波长随着溶剂极性的改变而发生变化，它们属于Class Ⅱ类型的混合价化合物；而C(CN)₃-桥联的Ru^ⅡRu^Ⅲ混合价配合物在近红外的吸收要强得多，且溶剂极性的改变对IVCT最大吸收波长基本无影响，它们属于介于价态定域与离域之间的混合价配合物。     

Ge2H2 a π-ligand in organometallic chemistry

η² π-Complexes of Ge₂H₂ with the organometallic fragments V(PH₃)₂(I)(CO)₂, Cr(CO)₄, Co(PH₃)₂(Cl) and M(PH₃)₂ (M = Ni, Pd, Pt) have been studied at the B3LYP level using the SBKJC relativistic effective core potentials and their associated basis sets on metals and iodine, and the 6-31G(d) basis set on all other elements. The transition metal fragments of V, Cr, Co, Ni, Pd and Pt were chosen based on known alkyne compounds. All the complexes are local minima for both the HGeGeH and GeGeH₂ isomers of the Ge₂H₂ ligand. The complexes containing GeGeH₂ isomer as a ligand are lower in energy than those with the HGeGeH ligand (except in the V complex in which the difference is only 1.0 kcal/mol). There is a net charge transfer from ligand to metal in complexes V-Co and from metal to ligand in late transition metal complexes (Ni-Pt).     

Reactions of cisplatin hydrolytes, cis-[Pt(15NH3)2(H2O) 2]2+, with N-acetyl-L-cysteine

The reaction of cis-[Pt(¹⁵NH₃)2(H₂O) ₂] ²⁺ (3) with N-acetylcysteine [H₃accys] was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. A mono-dentate sulfur-boundplatinum(II) product cis-[Pt(¹⁵NH₃)₂(H₂O)(H2accys-S)]⁺ (7) and six-membered che-late ring complex cis-[Pt(¹⁵NH₃)₂ (Haccys-S,O)] (8) were formed in solution. The dinuclear sulfur-bridged complex 9, giving a broad peak in ¹⁵N NMR, was also observed, but only present in very tiny amounts. The mass spectrometry (ES-MS) was undertaken from this re action, and the product detected was only the dinuclear sulfur bridged platinum species and species related to it by ammine loss.     

Oxidative addition of dihydrogen to Ni(II) complexes.ab initio MO/MP4 calculations of the electronic structure of NiH2Cl2(PH3)2 complex

Electronic state d⁶ Ni(IV) in the complex [NiH₂Cl₂(PH₃)₂] was studied by means ofab initio MO/MP4 calculations.     

Phosphine σ-sydnonyl complexes of Ni,Pd, and Pt

3-R"-4-Bromosydnones 1 (R" = Me) and 2 (R" = Ph) react with complexes Ì(PR₃)_n (M = Ni, Pd, Pt) to form mononuclear phosphine -sydnonyl d⁸-complexes of trans-configuration MBr(3-R"-sydnon-4-yl)(PR₃)₂: 3, 4 (Ì = Ni, R" = Ph); 5 (M = Pd, R" = Me); 6a (M = Pd, R" = Ph); 7 (M = Pt, R" = Ph). In the reaction of bromosydnone 2 with Pd(PPh₃)₄, the cis-complex PdBr(3-Ph-sydnon-4-yl)(PPh₃)₂ (6b) is formed initially; 6b rearranges in solution to give trans-complex 6a. On heating in THF, complex 6a is converted into the binuclear [PdBr(3-phenylsydnon-4-yl)(PPh₃)]₂ complex (8). The reaction of 4-chloromercurio-3-phenylsydnone (10) with Ni(PEt₃)₄, Pd(PPh₃)₄, and Pt(PPh₃)₄ gives mononuclear NiCl(3-phenylsydnon-4-yl)(PEt₃)₂ complex (11), binuclear [PdCl(3-phenylsydnon-4-yl) (PPh₃)]₂ complex (14), and cis- and trans-bimetallic PtCl(3-phenylsydnon-4-ylmercurio)(PPh₃)₂ complexes 15a and 15b, respectively. UV irradiation of 15a and 15b in a benzene solution induces redox demercuration to yield the PtCl(3-phenylsydnon-4-ylcarbonyl)(PPh₃)₂ complex (16). In carbonylation of complexes 3, 6, and 7, CO insertion into the M--C bond occurred to form the corresponding acyl derivatives MBr(3-phenylsydnon-4-ylcarbonyl)(PR₃)₂ (17--19).     

Synthesis and reaction chemistry of 4-nitrile-substituted NCN-pincer palladium(II) and platinum(II) complexes (NCN = [NC-4-C6H2(CH2NMe2)2-2,6])

Nitrile-functionalized NCN-pincer complexes of type [MBr(NC-4-C₆H₂(CH₂NMe₂)₂-2,6)] (6a, M = Pd; 6b, M = Pt) (NCN = [C₆H₂(CH₂NMe₂)₂-2,6]⁻) are accessible by the reaction of Br-1-NC-4-C₆H₂(CH₂NMe₂)₂-2,6 (2b) with [Pd₂(dba)₃ · CHCl₃] (5a) (dba = dibenzylidene acetone) and [Pt(tol-4)₂(SEt₂)]₂ (5b) (tol = tolyl), respectively. Complex 6b could successfully be converted to the linear coordination polymer {[Pt(NC-4-C₆H₂(CH₂NMe₂)₂-2,6)](ClO₄)}_n (8) upon its reaction with the organometallic heterobimetallic π-tweezer compound {[Ti](μ-σ,π-CCSiMe₃)₂}AgOClO₃ (7) ([Ti] = (η⁵-C₅H₄SiMe₃)₂Ti).The structures of 6a (M = Pd) and 6b (M = Pt) in the solid state are reported. In both complexes the d⁸-configurated transition metal ions palladium(II) and platinum(II) possess a somewhat distorted square-planar coordination sphere. Coordination number 4 at the group-10 metal atoms M is reached by the coordination of two ortho-substituents Me₂NCH₂, the NCN ipso-carbon atom and the bromide ligand. The NC group is para-positioned with respect to M.     

Synthesis, characterization and thermal properties of cobalt(II), nickel(II) and copper(II) complexes of 2,6-bis(3,4,5-trimethyl-N-pyrazolyl)pyridine): the crystal structure of [Co(btmpp)(H2O)2(NO3)]NO3

Co(II), Ni(II) and Cu(II) nitrate complexes with btmpp, namely ([Co(btmpp)(H₂O)₂(NO₃)]NO₃ (1), [Ni(btmpp)(H₂O)(NO₃)]NO₃ (2) and [Cu(btmpp)(MeOH)(NO₃)]NO₃ (3), where btmpp = 2,6-bis(3,4,5-trimethyl-N-pyrazolyl)pyridine), have been synthesized and characterized by physicochemical and spectroscopic methods. The crystal structure of complex 1 has been determined by single crystal diffraction at 100K. In all the complexes, btmpp is coordinated in a tridentate mode through its nitrogen atoms. One of the nitrates in complex 1 is terminally bonded to the metal center through the oxygen atom, whereas the other one is out of the coordination sphere. The Co(II) atom in complex 1 is hexa-coordinated with a CoN₃O₃ distorted octahedral environment. Decomposition of three complexes was analyzed thermogravimetrically. All three complexes decompose similar to explosive material.     

Chelate structures of 5-(H/Br)-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazones (H2L): Synthesis and structural characterizations of [Ni(L)(PPh3)] and [Ru(HL)2(PPh3)2]

The reactions of 5-R-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazone {R: H (L¹); Br (L²)} with [M^II(PPh₃)nCl₂] (M = Ni, n = 2 and M = Ru, n = 3) in a 1:1 molar ratio have given stable solid complexes corresponding to the general formula [Ni(L)(PPh₃)] and [Ru(HL)₂(PPh₃)₂]. While the 1:1 nickel complexes are formed from an ONS donor set of the thiosemicarbazone and the P atom of triphenylphosphine in a square planar structure, the 1:2 ruthenium complexes consist of a couple from each of N, S and P donor atoms in a distorted octahedral geometry. These mixed-ligand complexes have been characterized by elemental analysis, IR, UV–Vis, APCI-MS, ¹H and ³¹P NMR spectroscopies. The structures of [Ni(L²)(PPh₃)] (II) and [Ru(L¹H)₂(PPh₃)₂] (III) were determined by single crystal X-ray diffraction.     

Synthesis and characterization of new sulfide aggregates of the type [{Pt2(μ3-S)2(P-P)2}M(C6F5)2] (M=Ni, Pd, Pt; P-P=2PPh3, 2PMe2Ph, dppf)

The reaction of [Pt₂(μ-S)₂(P-P)₂] (P-P=2PPh₃, 2PMe₂Ph, dppf) [dppf=1,1^′-bis(diphenylphosphino)ferrocene] with cis-[M(C₆F₅)₂(PhCN)₂] (M=Ni, Pd) or cis-[Pt(C₆F₅)₂(THF)₂] (THF=tetrahydrofuran) afforded sulfide aggregates of the type [{Pt₂(μ₃-S)₂(P-P)₂}M(C₆F₅)₂] (M=Ni, Pd, Pt). X-ray crystal analysis revealed that [{Pt₂(μ₃-S)₂(dppf)₂}Pd(C₆F₅)₂], [{Pt₂(μ₃-S)₂(PPh₃)₂}Ni(C₆F₅)₂], [{Pt₂(μ₃-S)₂(PPh₃)₂}Pd(C₆F₅)₂] and [{Pt₂(μ₃-S)₂(PMe₂Ph)₂}Pt(C₆F₅)₂] have triangular M₃S₂ core structures capped on both sides by μ₃-sulfido ligands. The structural features of these polymetallic complexes are described. Some of them display short metal-metal contacts.