Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).     

钯(Ⅱ)-芳香氮碱-氨基酸三元配合物中的电子效应和芳环堆积作用

用pH-电位滴定法测定了Pd(L)(Aa)⁺三元配合物及相应的二元配合物,在25±0.5℃,30%的乙醇水溶液(体积分数),I=0.1(KNO₃)条件下的稳定常数及表征常数。其中L=邻菲罗啉(phen)、苯并咪唑邻菲罗啉(PIP)、邻菲罗啉-5,6-二酮(dophen)、2,9-二甲基邻菲罗啉(dmphen)和联吡啶3,3′-二羧酸(BDA);Aa为甘氨酸(gly)、苯丙氨酸(phe)、酪氨酸(tyr)、S-苄基-半胱氨酸(bcys)、谷氨酰胺(glu)和γ-谷氨酰-α-萘胺(gnapa)。从配合物配体间的电子效应和芳环堆积等观点对配合物的附加稳定性进行了讨论,并计算了电子效应和芳环堆积效应各自对三元配合物附加稳定性的贡献。     

meso-四(邻烷氧基苯基)卟啉合钴的合成、表征和性能研究

合成了meso-四(邻烷氧基苯基)卟啉合钴配合物10个,其中未见文献报道的新化合物8个，研究了其合成、分离、纯化方法,首次得到了该系列化合物的晶体或固体。用¹H NMR、MS、IR、UV、元素分析等表征确证了其结构,报道和解析了该类卟啉钴配合物的¹H NMR特殊波谱现象。用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现6个配合物具有液晶性。研究了烷氧基链长、金属离子和分子空间结构对卟啉液晶性能的影响,烷氧基链长的增加、金属配合物的形成有利于液晶性能的改善。     

Hydrothermal synthesis, crystal structures and luminescent properties of two new Ln(III)–succinate (Ln=Eu, Tb) complexes exhibiting three dimensional networks

Two new coordination polymers, [Eu₂(L)₃(H₂O)₂]_n 1 and {[Tb₂(L)₃(H₂O)₂]·H₂O}_n 2, (H₂L=succinic acid) have been synthesized by the reaction of H₂L with nitrate salts of Eu(III) or Tb(III) under hydrothermal conditions. The X-ray diffraction analysis reveals that the two complexes are constructed by L bridging the chains of edge-sharing EuO₈(H₂O) or TbO₈(H₂O) polyhedra to form 3D network structure. 1 and 2 possess different topological structures due to the difference in the conformations of L. The solid photoluminescence of 1 and 2 was also investigated in room temperature.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

中性配合物Cr(acac)_3、mer-和fac-[Cr(bza)_3]的光学拆分

本文用新方法合成了Cr(bza)_3,改进了其mer-、fac-异构体的分离方法;增大了Cr(acac)_3的化学拆分量(1.5g)。试制了DBT(二苯甲酰-d-酒石酸)吸附型手性固定相(CSP),并成功地用于色谱拆分标题配合物的对映体,mer-[Cr(bza)_3]的部分拆分是首次发现的,其他配合物的拆分结果均优于文献方法。根据mer-[Cr(bza)_3)拆分流出液前、后组分的CD光谱,指定了其对映体绝对构型。还讨论了DBT吸附型CSP的拆分效能和色谱特性。     

Synthesis and crystal structures of heterobimetallic Fe-Cd,Fe-Zn,and Fe-In complexes containing hemilabile phosphorus/oxygen and silicon/oxygen bridging ligands

The reactions of K[Fe{Si(OMe)₃}(CO)₃(PY)][PY=Ph₂PCH₂C(O)Ph, Ph₂PCH₂C(O)[(-C₅H₄)FeCp] (Cp=⁵-C₅H₅), Ph₂P(CH₂)₂CN] with CdCl₂·2.5H₂O, ZnX ₂ (X=Cl, I) or InCl₃ afforded Fe-Cd-Fe or Fe-M(-X)₂ M-Fe (M=Cd, Zn, In;X=Cl, I) and Fe-InCl₂ complexes. Some of them contain an unusual and labile -²-SiO alkoxysilyl bridge which may be associated with a bridging mode for the ketophosphine ligand (first such example structurally established), thus providing original results in bimetallic chemistry on the intramolecular coordination of oxygendonor functions ofchemically different hemilabile ligands firmly attached to a neighboring metal center. The structures of the trinuclear complex (3), of the chlorobenzene solvate of the tetranuclear complex (4a·C₆H₅Cl) and of [mer-(OC)₃{(EtO)₃Si} (4e) have been determined by X-ray diffraction. Crystals of 3 are orthorhombic, space groupPbcn, witha=19.010(4),b=11.766(5),c=26.998(7)Å, andZ=4. Crystals of4a·C₆H₅Cl are monoclinic, space groupC2/c witha=22.455(3),b=17.680(2),c=16.627(4)Å, =90.80(4)°, andZ=4. Crystals of4e are monoclinic, space groupC2/c witha=25.392(5),b=18.554(6),c=16.28(1)Å, =120.73(3)°, andZ=4. The structures were solved using direct methods and Fourier difference techniques and refined by blocked full-matrix least squares toR=0.035 (R _w =0.049) for 2719 observed reflections, toR=0.042 (R _w =0.056) for 3082 observed reflections, and toR=0.057 (R _w =0.075) for 1850 observed reflections for3, 4a·C₆H₅Cl and4e, respectively. The Fe-Zn complexes (9a), (9b) and (9c) were prepared and characterized by spectroscopic methods.Part 21 in the Series: Complexes with Functional Phosphines. Part 20: P. Braunstein, S. Coco Cea, A. DeCian, and J. Fischer (1992).Inorg. Chem. 31, 4203.     

苯二甲酰基桥联铁硫配合物［（μ－RS）Fe_2（CO）_6］_2（μ－OCC_6

通过由Ｆｅ３（ＣＯ）１２、ＲＳＨ和Ｅｔ３Ｎ所形成的［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］Ｅｔ３ＮＨ于室温下分别与对或间苯二甲酰氯的原位反应，首次合成６个结构新颖的苯二甲酰基桥联铁硫配合物［（μ－ＲＳ）·Ｆｅ２（ＣＯ）６］２（μ－ｐ－ＯＣＣ６Ｈ４ＣＯ－ｐ－μ）（Ｒ＝Ｅｔ，ｎ－Ｂｕ，ｔ－Ｂｕ）以及［（μ－ＲＳ）Ｆｅ２（ＣＯ）６］２（μ－ｍ－ＯＣＣ６Ｈ４ＣＯ－ｍ－μ）（Ｒ＝ｎ－Ｐｒ，ｎ－Ｂｕ，ｔ－Ｂｕ）。经元素分析、ＩＲ光谱及１ＨＮＭＲ表征了它们的结构，并讨论了产物的生成过程。此外，还提出了合成对苯二甲酰氯的一种新方法。     

Zweikernige silylenverbrückte Cyclopentadienylrhodiumbis(ethen)-Komplexe,photochemische Reaktion mit Benzolderivaten und selektiver Einschluß von Methylcyclopentan in das Kristallgitter von [Me2Si{3-But-C5H3Rh(C2H4)2}2]

Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me₂Si{3-Bu^t-C₅H₃Rh(C₂H₄)₂}₂] By reaction of [{(C₂H₄)₂RhCl}₂] with Na₂[Me₂Si(C₅H₄)₂] or with Li₂[Me₂Si(3-Bu^t-C₅H₃)₂] in THF the dinuclear silylene bridged complexes [Me₂Si{C₅H₄Rh(C₂H₄)₂}₂] 1 and [Me₂Si{3-Bu^t-C₅H₃Rh(C₂H₄)₂}₂] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η³:η³ benzene complex [Me₂Si(C₅H₄Rh₂)₂C₆H₆] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 .     

Synthesis and characterization of a new isocyanato carborane anion [7-OCN-7-CB10H12]; study on its reactivity toward amino containing compounds

The new isocyanato carborane anion, [7-OCN-7-CB₁₀H₁₂]⁻ was prepared by the reaction of 7-H₃N-7-CB₁₀H₁₂ with triphosgene in the presence of triethylamine. The structure of this compound was established by ¹H, ¹¹B and ¹³C NMR as well as IR spectroscopy. The reactivigty of this compound with a series of organic amines was investigated. The resulting ureas were obtained in good to excellent yields. This approach is suitable for development of compounds for use in tumor selective Boron Neutron Capture Therapy (BNCT).