Synthetically tailoring diamondoids for semiconductor applications

本提案描述了量身定做的功能化钻石颗粒(纳米钻石颗粒)的制备，这种颗粒将由现有的和--这是我们动机的一部分--新的化学路线制备。这些新的纳米金刚石衍生物的性质将与研究单位内具有光谱和理论取向的基团一起确定。这些纯净和均匀的化合物的现场选择性合成具有挑战性，因为目前只有少量较高的金刚烷类化合物可用，即它们需要高产量和高选择性的方法。因此，协同机理研究的目的还在于确定烷基阳离子作为主要功能化中间体的作用和结构。我们的合成工作将首先集中在金刚烷、[121]十四烷和[1(2，3)4]戊烷中的金刚烷硫醇，以用于随后制备金属杂化金刚烷簇合物，特别是贵金属簇合物。其次，我们概述了用于荧光应用的(硫代)醚、酮和硫酮形式的内外掺杂菱形体的制备方法。将制备SP2-SP3结(不饱和金刚石)(乙烯基、炔基和芳基衍生物)，用于探测饱和-不饱和界面的电子性质，这通常是导致钻石中sp2缺陷位置的不寻常性质的原因。

The present proposal describes the preparation of tailor-made functionalized diamondoids (nanometer-sized diamond particles) that will be prepared by both existing and – and this is part of our motivation – new chemical routes. The properties of these new nanodiamond derivatives will be determined together with the spectroscopically and theoretically orientated groups within the research unit. The site-selective synthesis of these pure and uniform compounds challenging because only small quantities of the higher diamondoids are currently available, i.e., they require high-yielding and highly selective approaches. Collaborative mechanistic studies therefore also aim at identifying the role and structures of alkane radical cations as key intermediates in the primary functionalizations of the diamondoids. Our synthetic efforts will first focus on diamondoid thiols from the group of adamantane, diamantane, triamantane, [121]tetramantane, and [1(2,3)4]pentamantane) for the subsequent preparation of metal-hybrid diamondoid clusters, in particular, noble metal clusters. Secondly, we outline the preparation of internally and externally doped diamondoids in form of their (thio)ethers, ketones, and thiones for fluorescence applications. sp2-sp3-Junctions (unsaturated diamondoids) will be prepared (vinyl, alkynyl and aryl derivatives) for probing the electronic properties at the saturation-unsaturation interface that is often made responsible for the unusual properties of sp2-defect sites in diamond.