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Development of Structurally Constrained Metal Clusters Leading to Functional Nano-Molecular Devices

结构约束金属簇的开发导致功能纳米分子器件

基本信息

批准号：
13304053
负责人：
TANASE Tomoaki
金额：
$ 34.94万
依托单位：
Nara Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2004
项目状态：
已结题

项目摘要

Linear transition-metal clusters have recently attracted increasing attention concerning their unique structural, optical, and electrochemical properties. Attempts to build up much expanded molecules with multi-functional metal-metal interactions are highly desired in relation to development of molecular-based electronic devices as well as to exploration of unprecedented physical and chemical behaviors. In this project, we have studied the syntheses, characterization, and reactivities of linear hexanuclear clusters. Reduction of Pt_3 complex 1 with NaBH_4 in E_tOH afforded the linear hexaplatinum cluster, [Pt_6(μ-H)(μ-dpmp)_4(RNC)_2(PF_6)_3 (3), whereas the analogous heterometallic cluster, [Pt_4Pd_2(μ-H)(μ-dpmp)_4(RNC)_2](PF_6)_3 (4), was synthesized from reaction of Pt_2Pd complex 2 with NaOMe ([PL_2M(μ-dpmp)_2(RNC)_2](PF_6)_2 (M=Pt (1), Pd (2); dpmp=bis(diphenyl- phosphinomethyl)phenylphosphine, RNC=organoisocyanide). Complex 3a (R=Xyl) is a trivalent, 86e-cluster and involves a linear Pt_6 core (Pt-Pt(central)=3.3092(5) Å, Pt-Pt(inner)=av. 2.733 Å, Pt-Pt(outer)= av. 2.704 Å) supported by four dpmp ligands and terminally coordinated by two isonitriles. The clusters 3a and 4a readily underwent two-electron oxidation to afford [Pt_4Pd_2(μ-dpmp)_4(RNC)_2](PP_6)_4 (M=Pt (5a), Pd (5b)). Reduction of 1 with NaBH_4 in DMF afforded dark green trihydride hexaplatinum complex, [Pt_6(μ-H)(H)_2(μ-dpmp)_4](PF_6) which was interestingly converted into neutral hexplatinum cluster with coordinatively unsaturated terminals, [Pt_6(μ-H)_2(μ-dpmp)_4] (6). The trihydride cluster readily reacted with Mel to give [Pt_6(μ-H)(I)_2(μ-dpmp)_4](PF_6). These linear clusters with hydrides could be of significant importance as reactive functional metal wires coupled with redox processes. The SAM's (self assembled monolayer) of bisisocyanide-linked 3a were prepared and characterized by electrochemical methods.

线性过渡金属簇合物因其独特的结构、光学和电化学性质而受到人们的广泛关注。构建具有多功能金属-金属相互作用的更大扩展分子的尝试对于开发基于分子的电子器件以及探索前所未有的物理和化学行为是高度期望的。在本计画中，我们研究了线型六核团簇的合成、表征及反应性。用NaBH_4在EtOH中还原Pt_3配合物1得到六铂线性簇合物[Pt_6（μ-H）（μ-dpmp）_4（RNC）_2（PF_6）_3（3），而类似的杂金属簇合物[Pt_4Pd_2（μ-H）（μ-dpmp）_4（RNC）_2]（PF_6）_3（4），由Pt_2Pd配合物2与NaOMe反应合成了[PL_2M（μ-dpmp）_2（RNC）_2]（PF_6）_2（M=Pt（1），Pd（2）; dpmp=双（二苯基膦甲基）苯基膦，RNC=有机异腈）。配合物3a（R=Xyl）是一个三价的~（86）e簇合物，中心Pt-Pt =3.3092（5）π，中心Pt-Pt =av. 2.733 μ m，Pt-Pt（外部）=平均值。2.704 π），其由四个DPMP配体支撑并由两个异腈末端配位。簇合物3a和4a容易发生双电子氧化，得到[Pt_4Pd_2（μ-dpmp）_4（RNC）_2]（PP_6）_4（M=Pt（5a），Pd（5 b））。1在DMF中用NaBH_4还原得到深绿色的三氢化六铂配合物[Pt_6（μ-H）（H）_2（μ-dpmp）_4]（PF_6），该配合物有趣地转化为具有配位不饱和末端的中性六铂簇合物[Pt_6（μ-H）_2（μ-dpmp）_4]（6）。三氢簇合物与Mel反应生成[Pt_6（μ-H）（I）_2（μ-dpmp）_4]（PF_6）。这些线性簇合物与氧化还原过程耦合的反应性功能金属线可能是显着的重要性。制备了双异氰酸酯连接的3a自组装单分子膜，并通过电化学方法对其进行了表征。