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.

线性过渡金属簇最近引起了人们对它们独特的结构，光学和电化学特性的越来越多的关注。在基于分子的电子设备的发展以及对前所未有的物理和化学行为的探索方面，高度期望与多功能金属相互作用建立大量扩展的分子的尝试。在这个项目中，我们研究了线性六核簇的合成，表征和反应性。在E_TOH中使用NABH_4的PT_3复合物减少了线性六链球菌簇，[PT_6（μ-H）（μ-DPMP）_4（rnc）_2（pf_6）_3（pf_6）_3（3） [pt_4pd_2（μ-h）（μ-dpmp）_4（rnc）_2]（pf_6）_3（4），是根据pt_2pd复合物与naome（[pl_2m（μ-dpmp）_2（RNC）_2（RNC）_2（RNC）_2]（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_2（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_6）（PF_2（Pf_6）（M = M = M = M = M = M = M = M = M） dpmp =双苯基磷酸，rnc =有机环氰化物）。 2.704Å）由四个DPMP配体支持，并由两个以异构体协调。 DMF中的NABH_4提供了深绿色的三氢化盐六边形复合物，[pt_6（μ-h）（H）_2（μ-DPMP）_4]（Pf_6）（PF_6），有趣地转化为中性六倍氨酸群，并以协调的未饱和末端聚类，[ （6）。三氢簇簇很容易与MEL反应，得到[PT_6（μ-H）（I）_2（μ-DPMP）_4]（PF_6）。这些带有氢化物的线性簇可能非常重要，因为反应性功能金属电线以及氧化还原过程。制备了双氰化物连接3A的SAM（自组装单层），并以电化学方法为特征。