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Complexes in which sp Carbon Chains span two Metals

Complexes in which sp Carbon Chains span two Metals
sp 碳链跨越两种金属的配合物
批准号:
0719267
负责人:
John Gladysz
金额:
$45.8万
依托单位国家:
美国
项目类别:
Continuing Grant
财政年份:
2007
资助国家:
美国
项目状态:
已结题
起止时间:
2007-08-01 至 2011-07-31

项目摘要

项目成果

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中文摘要
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英文摘要
The objective of this project is to synthesize complexes in which wire-like sp-hybridized carbon chains span two transition metal fragments, and to conduct detailed studies of their chemical and physical properties. At very long chain lengths, such materials bear a strong conceptual relationship to diamond and graphite, the classical three- and two-dimensional sp3 and sp2-hybridized polymeric carbon allotropes. They are also much more stable than analogs with organic endgroups. Progressively more complex architectures based upon such building blocks will be sought. In one effort, complexes with C32-C40 chains, in which the metal-metal distances would surpass 5 nm, will be targeted; those with C24-C28 chains are easily isolable and stable to 140 C. In another effort, the Cx chain will be sterically protected via two flexible sp3 carbon chains that span donor atoms on each terminus. When sufficiently long, these adopt chiral double helical conformations, much like the insulation about household electrical wire. The redox properties of such species will be studied; it is anticipated that the stabilities of mixed valence radical ions will be enhanced. Other approaches to sterically shielded sp chains involving rotaxanes will be investigated. In another effort, lateral arrays or "bundles" of such complexes with parallel Cx chains will be synthesized. These can be viewed as multi-stranded molecular wires. In another effort, well-defined longitudinally extended arrays, such as PtCxPtCxPtCxPt species, will be prepared. "Alligator clips" will be introduced on the terminal platinum atoms such that single-molecule conductivities can be measured. Reactions with chelating diphosphines may introduce "kinks" that might allow (under appropriate conditions) reductive eliminations to PtC3xPt species or oxidative couplings to polygons that contain platinum atoms at each corner. Polygons will also be prepared by oxidative couplings of monoplatinum species. Attempts will be made to extrude the platinum atoms, generating a cyclocarbon Cx (a monomeric carbon allotrope). Reactions of the C=C moieties will be investigated, such as trimerizations to hexasubstituted benzenes and metatheses to give odd-carbon species M(C=C)n'C=M'. In collaborative efforts, the NLO and photophysical properties of each family of complexes will be characterized. Particular attention will be given to defining chain length effects and chain-chain interactions. A detailed knowledge of how to engineer these wire-like unsaturated molecules into a variety of sophisticated architectures will result.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor John A. Gladysz, of the Department of Chemistry at Texas A&M University. Professor Gladysz and his students are exploring the synthesis and properties of molecules containing extended carbon chains capped by metal atoms. These systems mimic all-carbon systems of considerable current interest. They are expected to display a variety of unusual properties of potential relevance in the design and construction of molecular wires, nonlinear optical materials, and other more complex molecular aggregates. Students involved in this project will have the opportunity to collaborate with students in Germany and with physical chemists specializing in the characterization of molecular materials.
期刊论文(15)
专著(0)
科研奖励(0)
会议论文
En route to diplatinum polyynediyl complexes trans,trans-(Ar)(R3P)2Pt(C≡C)nPt(PR3)2(Ar): Untold tales, including end-group strategies
通往二铂聚炔二基配合物 trans,trans-(Ar)(R3P)2Pt(C−C)nPt(PR3)2(Ar) 的途中:不为人知的故事,包括端基策略
DOI: 10.1351/pac200880030459
发表时间: 2008
期刊: Pure and Applied Chemistry
影响因子: 1.8
作者: [Stahl, Jürgen, Bohling, James C., Peters, Thomas B., de Quadras, Laura, Gladysz, John A.]
通讯作者: Gladysz, John A.
Syntheses and structural analyses of chiral rhenium containing amines of the formula (η5-C5H5)Re(NO)(PPh3)((CH2)nNRR′) (n=0, 1)
含胺手性铼的合成和结构分析 (η5-C5H5)Re(NO)(PPh3)((CH2)nNRRâ²) (n=0, 1)
DOI: 10.1016/j.ica.2009.03.047
发表时间: 2010
期刊: Inorganica Chimica Acta
影响因子: 2.8
作者: [Seidel, Sabine N., Prommesberger, Markus, Eichenseher, Sandra, Meyer, Oliver, Hampel, Frank, Gladysz, John A.]
通讯作者: Gladysz, John A.
Dreifach-verbrückte Diphosphane mit von innen nach außen invertierender Konfiguration
Dreifach-verbrückte Diphosphane mit von innen nach auàen invertierender 配置
DOI: 10.1002/ange.201100893
发表时间: 2011
期刊: Angewandte Chemie
影响因子: --
作者: [Stollenz, Michael, Barbasiewicz, Michał, Nawara-Hultzsch, Agnieszka J., Fiedler, Tobias, Laddusaw, Ryan M., Bhuvanesh, Nattamai, Gladysz, John A.]
通讯作者: Gladysz, John A.
sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(CC)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents
sp 碳链被 sp3 碳双螺旋包围:线状 Pt(CîC)nPt 部分,由两个带有杂原子或烷基取代基的 α,β-二膦跨越
DOI: 10.1039/b708690n
发表时间: 2007
期刊: New Journal of Chemistry
影响因子: 3.3
作者: [de Quadras, Laura, Bauer, Eike B., Stahl, Jürgen, Zhuravlev, Fedor, Hampel, Frank, Gladysz, John A.]
通讯作者: Gladysz, John A.
10
    Gyroscope Like Metal Complexes
    • 批准号:
      1900549
    • 项目类别:
      Standard Grant
    • 资助金额:
      $48.5万
    • 财政年份:
      2019
    • 负责人:
      John Gladysz
    • 依托单位:
    Gyroscope-Like Metal Complexes
    • 批准号:
      1566601
    • 项目类别:
      Standard Grant
    • 资助金额:
      $42.0万
    • 财政年份:
      2016
    • 负责人:
      John Gladysz
    • 依托单位:
    WIRE-LIKE and GYROSCOPE-LIKE ORGANOMETALLIC COMPLEXES
    • 批准号:
      1153085
    • 项目类别:
      Continuing Grant
    • 资助金额:
      $39.0万
    • 财政年份:
      2012
    • 负责人:
      John Gladysz
    • 依托单位:
    Complexes in Which sp Carbon Chains Span Two Transition Metals
    • 批准号:
      9732605
    • 项目类别:
      Standard Grant
    • 资助金额:
      $48.9万
    • 财政年份:
      1998
    • 负责人:
      John Gladysz
    • 依托单位:
    国内基金
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    类肌动蛋白Mreb在Spiroplasma sp.DGKH1形态变化中的功能研究
    • 批准号:
      2026JJ82692
    • 项目类别:
      省市级项目
    • 资助金额:
      --
    • 批准年份:
      2026
    • 负责人:
      张凯华
    • 依托单位:
    基于PVA纤维捕集-SP-ICP-TOF的深穿透土壤纳米颗粒矿致异常识别方法研究
    基于SP1/ZDHHC8轴调控GPX4棕榈酰化探讨银星养脑片干预脑缺血再灌注后神经元铁死亡的作用机制
    • 批准号:
      2026JJ81757
    • 项目类别:
      省市级项目
    • 资助金额:
      --
    • 批准年份:
      2026
    • 负责人:
      吴兵兵
    • 依托单位: