Ethynyl(di)thiolates and -(di)selenolates: from the synthesis to potential applications

乙炔基（二）硫醇盐和-（二）硒醇盐：从合成到潜在应用

• 批准号: 423432238
• 负责人: Professor Dr. Uwe Ruschewitz
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/423432238?language=en
• 关键词: Ethynyl; di; thiolates; selenolates; synthesis

For many years, the Ruschewitz group has been investigating binary and ternary acetylides of alkali and alkaline earth metals, whereby in particular the ternary alkali metal transition metal acetylides synthesized by us represent an interesting class of materials at the border between ionic and semiconducting properties. Since 2018, we have succeeded for the first time in synthesizing acetylides of selenium (A(I)SeC2H with A(I) = Na, K, Rb, Cs), which contain the previously unknown linear –SeC2H anion in crystalline form. In the meantime, we were also able to present compounds with the composition A(I)SC2H (A(I) = Na, K, Rb, Cs), which contained the -SC2H anion, isolobal to ubiquitous thiocyanate. In this project, transition metal compounds with these anions shall be synthesized for the first time and the properties of these two ligands in complexes will be investigated, always in comparison to the well-known thiocyanate and selenocyanate ligands. Investigations on the thermal stability of these anions, their reactivity with respect to oxidation and the formation of dimers or polymers are also aims of this work. In 2022 we published Li2[SeC2Se] x 2NH3, which contains the extremely unusual ("exotic") dianion -Se-C2-Se-. This is also present in compounds of the composition A(I)2E2C2 with A(l) = Na, K, Rb, Cs and E = Se, Te. By oxidation with iodine or bromine, SeCx polymers should be accessible, for which an increased conductivity is expected and which could possibly be interesting in the field of optoelectronics. Similarly, high conductivities are expected for coordination polymers based on aromatic bis(ethinylselenolates), which we also want to synthesize in the proposed project for the first time. Thus, based on the compounds described in the first project, this follow-up proposal aims to show ways how materials can be obtained, for which interesting applications, e.g. in the field of optoelectronics, are to be expected. In addition to the planned syntheses and analyses, the project also includes accompanying quantum mechanical calculations on individual molecular fragments as well as extended solids.

多年来，Ruschewitz小组一直在研究碱金属和碱土金属的二元和三元乙炔化物，其中特别是我们合成的三元碱金属过渡金属乙炔化物代表了一类有趣的材料，介于离子和半导体性质之间。自2018年以来，我们首次成功合成了硒的乙炔化物（A（I）SeC 2 H，其中A（I）= Na，K，Rb，Cs），其含有以前未知的线性-SeC 2 H阴离子晶体形式。与此同时，我们还能够提出具有组成A（I）SC2 H（A（I）= Na，K，Rb，Cs）的化合物，其含有-SC2 H阴离子，与普遍存在的硫氰酸根等瓣。在该项目中，将首次合成具有这些阴离子的过渡金属化合物，并将研究这两种配体在配合物中的性质，始终与众所周知的硫氰酸盐和硒氰酸盐配体进行比较。这些阴离子的热稳定性，它们的氧化反应性和二聚体或聚合物的形成的调查也是这项工作的目的。在2022年，我们发表了Li 2 [SeC 2Se] x 2NH 3，它含有极不寻常的（“外来的”）二价阴离子-Se-C2-Se-。这也存在于组成A（I）2 E2 C2的化合物中，其中A（I）= Na、K、Rb、Cs，并且E = Se、Te。通过用碘或溴氧化，SeCx聚合物应该是可获得的，预期其电导率增加，并且其可能在光电子学领域中是令人感兴趣的。同样，高电导率的配位聚合物的基础上的芳香族双（乙炔基硒），我们也希望在拟议的项目中首次合成。因此，基于第一个项目中描述的化合物，该后续提案旨在展示如何获得材料的方法，预计这些材料将在光电子学领域等有趣的应用。除了计划中的合成和分析外，该项目还包括对单个分子片段以及扩展固体的量子力学计算。