5位芘取代的三芳基吡唑啉化合物的光物理行为

合成了化合物 1 ,3 二苯基 5 ( 1 芘基 ) 2 吡唑啉 (DPPP) .由于 5位大取代基的存在 ,使整个分子不在同一平面 ,导致吡唑啉化合物光物理性质的改变 .DPPP光物理行为的研究表明 :即使在较低的浓度下 ( c=1 .0 8× 1 0 -5 mol·L-1) ,DPPP分子间也易生成电荷转移络合物 ;其荧光光谱表现出明显的溶剂极性效应、浓度效应和温度效应 ,不同的环境条件下可发射芘单体的荧光、分子内电荷转移络合物的荧光及分子间电荷转移络合物的荧光 .     

金属离子络合物在荧光分子开关中的作用

金属离子络合物是荧光分子开关的一个重要组成部分。它作为荧光分子开关的组件具有灵敏度高、简单、可靠等特点。金属离子络合物既可以用作具有延迟发射的荧光团，也可以用作受体（主要接受阴离子客体），还可同时起双重作用。因而在生命科学、信息科学、环境分析、临床医学和显微技术等领域得到了广泛的应用。本文对近年来的有关科研成果进行了综述。     

烷烃和胺类分子对电子激发态CH(A~2Δ和B~2Σ~-)自由基猝灭

用266nm激光光解CHBr_3分子产生CH(A,B)态自由基,通过测量CH(A,B→X)自发辐射的时间分辨信号测定室温下(CH_3)_2NH、(C_2H_5)_2NH、(C_2H_5)_3N、n-C_5H_(12)、n-C_6H_(14)和n-C_7H_(16)对CH(A,B,v'=0)的猝灭速率常数.发现猝灭速率常数与猝灭剂烷烃分子中的C-H键数近似成线性关系,但对大的烷烃分子,这种增加逐渐趋缓.用碰撞络合物模型计算胺类分子及烷烃分子与CH形成碰撞络合物时的生成截面,结果表明,在电子激发态CH自由基的猝灭过程中,碰撞对子间的多极相互吸引势和色散力作用势可能起重要作用.     

CO2与HCN,NH3,H2O分子络合物的从头计算研究

用ab initio能量梯度法(3-21G基组)分别优化CO_2与HCN、NH_3、H_2O_3个分子络合物的平衡几何构型。结果表明HCN、NH_3和H_2O中的N或O原子与CO_2中的C原子之间形成较弱的范德华键,三者的范德华键键长分别为0.2865、0.2775、0.2543nm,稳定化能分别为14.8、27.0、31.2kJ·mol~(-1),3个分子络合物的构型都呈T型,对3个分子络合物的稳定化能的能量分解研究表明它们的形成主要靠静电作用能。     

Rotaxane络合物研究新进展

Rotaxane是在带有长链的分子上套入环状化合物的特铁络合物。本文综述了rotaxane络合物,特别是环状化合物为环糊精( cyclodextrin, CD)的rotaxane-CD络合物的组成、合成,一些性质和应用以及研兄方法,并提出了应予重视的研完方面。     

双核过渡金属络合物引发氮分子活化研究

将自然界资源丰富但化学性质上极其惰性的氮气分子在温和条件下转化为氨及其他含氮化合物,具有非常重要的意义。过渡金属络合物引发氮分子的活化及官能化已成为现代工业固氮的一大研究热点。本文回顾了氮分子与双核过渡金属络合物结合的键型模式,总结了影响氮分子活化的诸多因素如配体调变效应、金属调变效应等,对双核过渡金属络合物引发的双氮裂解、双氮官能化及CO/CO2协助双氮活化官能化等反应的实验与理论研究现状和进展进行了简要综述,并对未来过渡金属络合物在氮分子固定的应用发展作了展望。     

酞菁-卟啉超分子的形成及光致电子转移过程

用吸收光谱的方法研究了溶液中四－（４’－Ｎ，Ｎ，Ｎ－三甲基）－苯氧基）酞菁季铵碘盐及它的锌络合物与四－（４’－磺酸基苯基）卟啉及它的锌络合物通过分子间自组装形成的新一类超分子排列的杂聚体，用Ｊｏｂ氏光度滴定的方法确定了它们的组成，为面对面的杂二聚体或三明治式的杂三聚体超分子排列，证实卟啉和酞菁的中心络合金属与溶剂分子之间的轴向配位是决定了卟啉，酞菁杂聚体的组成，发现在超分子体系中卟啉与酞菁能互相猝     

β环糊精的双核铜络合物对芳香基氨基酸分子识别的研究

用荧光分光光度法和紫外分光光度法测定了β－环糊精双核铜络合物（Ｃｕ２－β－ＣＤ）在强碱性溶液中与氨基酸的超分子作用，发现Ｃｕ２－β－ＣＤ与芳香基氨基酸的荧光光谱和紫外光谱发生明显变化，Ｃｕ２－β－ＣＤ对于芳香基氨基酸具有分子识别作用，对于酪氨酸和苯丙氨酸，主客体间形成超分子络合物的化学计量比为１：４．有Ｓｃａｔｃｈａｒｄ方程或Ｌｉｎｅｗｅａｖｅｒ－Ｂｕｒｋ曲线分别了它们的物理常数，推测Ｃｕ２－β２     

过渡金属的分子氢(η~2-H_2)络合物

<正> 金属对分子H_2的活化反应,在应用科学及理论科学中均为重要的化学反应。H—H键是一强健(键能为431240.4J/mol)。因此H_2分子对不饱和物及其它化合物的加成反应,必须通过金属中心(M)的催化活化,形成碱性中间物M,即金属一分子H_2络合物(以下简称为分子H_2络合物),随后H—H键断裂形成金属氢化物MH。这一过程在催化加氢反应中起着重要作用。它可按两种方式进行:     

芳基重氮盐及其18-冠醚-6络合物的低频红外光谱

本文合成了九种不同取代基的苯基四氟硼酸重氮盐及其与18-冠醚-6形成的分子络合物, 考察它们的低频红外光谱, 讨论这类络合物的成键状况。     

From molecules to aggregates

The preparation of organometallic oxides, imides and nitrides is described. The molecular structures of these compounds resemble those found in binary systems. However, due to the organic envelope of the molecular solids, they are soluble in organic solvents, easy to crystallize and unambiguously characterizable by single X-ray structural analysis and NMR investigations. Moreover, inorganic oxides can be incorporated in organometallic phosphonates or organoalumoxanes. Herein we describe the organometallic phosphonates as hosts with a hydrophobic exterior.     

Organometallic chemistry related to applications for microelectronics in Japan

This is meant to be a brief overview of the developments of research activities in Japan on organometallic compounds related to their use in electronic and optoelectronic devices. The importance of organometallic compounds in the deposition of metal and semiconductor films for the fabrication of many electronic and opto-electronic devices cannot be exaggerated. Their scope has now extended to thin-film electronic ceramics and high-temperature oxide superconductors. A variety of organometallic compounds have been used as source materials in many types of processing procedures, such as metal–organic chemical vapor deposition (MOCVD), metalorganic vapor-phase epitaxy (MOVPE), metal–organic molecular-beam epitaxy (MOMBE), etc. Deposited materials include silicon, Group III–V and II–VI compound semiconductors, metals, superconducting oxides and other inorganic materials. Organometallic compounds are utilized as such in many electronic and optoelectronic devices; examples are conducting and semiconducting materials, photovoltaic, photochromic, electrochromic and nonlinear optical materials. This review consists of two parts: (I) research related to the fabrication of semiconductor, metal and inorganic materials; and (II) research related to the direct use of organometallic materials and basic fundamental research.     

The chemistry of (1-azabuta-1,3-diene)tricarbonyliron(0) complexes

In this review, an overview of synthetic and structural aspects of 1-azabuta-1,3-diene complexes of iron is given and the reactivity of these complexes is discussed with regard to inorganic, organometallic, organic and stereochemical aspects of their chemistry. Their application in the synthesis of organic and organometallic target compounds, or as transfer reagents of the tricarbonlyiron(0) moiety is demonstrated.     

Crystal synthesis of hybrid organometallic-inorganic hydrogen bonded salts of acid oxoanions

Partially deprotonated inorganic oxoanions derived from sulfuric and phosphoric acids have been used to assemble organometallic cations in inorganic-organometallic hybrid systems. The organometallic sandwich cations [(eta(5)-C(5)H(5))(2)Co]+, [(eta(5)-C(5)Me(5))(2)Co]+ and [(eta(5)-C(5)Me(5))(2)Fe]+ have been used because they do not interfere with hydrogen bonding formation forcing self-assembling of the inorganic acids anions HSO(4)(-) and H(2)PO(4)(-) into hydrogen bonded mono- and bi-dimensional networks.     

Speciation and Bioavailability:Present Status and Future Trend

Speciation analysis is nowadays performed routinely in environmental chemistry to control the quality of the environment and to study the behavior of inorganic speciation and organometallic compounds.     

芳基钌抗癌化合物的研究进展

无机药物化学领域正在快速发展,尤其是有机金属配合物作为癌症的治疗和诊断试剂有很大的潜力.芳基钌配合物中芳基对抗癌活性有重要影响,并能调控配合物金属中心的热力学和动力学性能.配合物的构效关系研究,对进一步合理设计/合成具有潜在药用价值的有机金属配合物至关重要.本文选取钌芳基配合物作为抗癌药物的具体实例进行讨论,重点介绍了多种芳基钌配合物的构效关系及抗癌机理.     

Special features of structural organization and magnetic properties of quasi-one-dimensional organoiron nanostructures on a silica support

Special features of the synthesis (constructing) of highly organized quasi-one-dimensional organoiron nanostructures were considered. For the first time magnetic properties of ferromagnetic nanostructures with a specified topology based on quasi-one-dimensional organometallic structures (of “pile“ type) fixed on an inorganic matrix were studied. The presence of an uncompensated antiferromagnetism arisen on plotting organoiron groups on a silica surface was experimentally found, and the obtained data showed the study of quasi-one-dimensional organometallic nanostructures fixed on a support to be promising for the spin electronics engineering.     

气体膨胀液体技术制备纳米微粒研究进展

近年来,利用气体膨胀液体的相行为已经开发了许多气体膨胀液体微粒制备方法,并已在制备无机、有机材料、有机金属固体、医药、电子等方面的微细颗粒方面得到广泛应用。本文介绍了气体膨胀液体制备纳米颗粒的研究和应用进展。     

Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports

Functionalizing inorganic particles with organic ligands is a common technique for heterogenizing organometallic catalysts. We describe how coordinating molecular platinum to silica nanoparticles functionalized with a high density of norbornene ligands causes unexpected latency of the catalytic activity in hydrosilylation reactions when compared to an identical reaction in which the norbornene is not tethered (2 % vs 97 % conversion in 1 h). Performing the hydrosilylation at elevated temperature (70 °C) suppresses this activity delay, suggesting the usefulness of this technique towards temperature-triggered catalysis. We demonstrate that this latency is related to ligand density on the particle surface, chemical structure of the norbornene, and silica nanoparticle topology. We also establish the benefit of this latency for triggered curing of silicone elastomers. Overall, our work establishes the non-innocent role of inorganic supports when functionalized with organometallic complexes.     

Bis(imidazolylidene)s as modular building blocks for monomeric and macromolecular organometallic materials

The synthetic and structural progression surrounding N-heterocyclic carbenes has given rise to great functional and architectural diversity in organometallic chemistry, catalysis, and materials science. The development of new, modular scaffolds for bridging transition metals is essential in order to expand the boundaries of these scientific areas. This Frontier article summarizes recent advances in the synthesis and study of ditopic ligands displaying two linearly opposed carbene moieties and emphasizes their versatility in the preparation of new organometallic and macromolecular materials. The conclusion previews their utility in conjugated organic/inorganic hybrid materials with potential applications in the emerging fields of molecular- and nanoelectronics.