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因其独特的结构、光学和电化学性质而受到越来越多的关注，在基于分子的电子器件的开发中，迫切需要尝试构建具有多功能金属-金属相互作用的扩展分子。以及探索前所未有的物理和化学行为在这个项目中，我们研究了 NaBH_4 还原 Pt_3 配合物 1 的合成、表征和反应性。 E_tOH 提供线性六铂簇，[Pt_6(μ-H)(μ-dpmp)_4(RNC)_2(PF_6)_3 (3)，而类似的异金属簇，[Pt_4Pd_2(μ-H)(μ-dpmp) _4(RNC)_2](PF_6)_3 (4)，由 Pt_2Pd 配合物 2 与NaOMe ([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=有机异氰化物)。配合物 3a ( R=Xyl) 是一个三价 86e 簇，包含线性 Pt_6 核心（Pt-Pt（中心）= 3.3092（5） Å，Pt-Pt（内部）= av. 2.733 Å，Pt-Pt（外部）= av. 2.704 Å）由四个 dpmp 配体支持，并由两个异腈进行末端配位。团簇 3a 和 4a 很容易进行双电子氧化，以提供[Pt_4Pd_2(μ-dpmp)_4(RNC)_2](PP_6)_4 (M=Pt (5a), Pd (5b)) 在 DMF 中用 NaBH_4 还原 1，得到深绿色三氢六铂络合物，[Pt_6(μ-)。 H)(H)_2(μ-dpmp)_4](PF_6) 有趣的是转换为中性具有配位不饱和末端的六铂簇，[Pt_6(μ-H)_2(μ-dpmp)_4] (6) 三氢化物簇很容易与 Mel 反应，得到 [Pt_6(μ-H)(I)_2(μ-dpmp)。 )_4](PF_6)。这些具有氢化物的线性簇作为与氧化还原过程相结合的反应性功能金属线可能具有重要意义。通过电化学方法制备并表征了二异氰化物连接的 3a 的组装单层。