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

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酰基化合物，特别是我们合成的三元碱金属过渡金属乙酰基化合物代表了一类介于离子和半导体性质之间的有趣材料。自2018年以来，我们首次成功合成了硒的乙酰基(A(I)SeC2H， A(I) = Na， K, Rb, Cs)，其中含有以前未知的线性-SeC2H阴离子。同时，我们还能够得到含有-SC2H阴离子的A(I)SC2H （A(I) = Na， K, Rb, Cs）组成的化合物，它与普遍存在的硫氰酸盐是异球形的。本项目将首次合成含这两种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，并与众所周知的硫氰酸盐和硒氰酸盐配体进行比较。研究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也是这项工作的目的。在2022年，我们发表了Li2[SeC2Se] x 2NH3，它含有极不寻常的（“外来的”）离子- se - c2 - se -。这也存在于组成A(I)2E2C2的化合物中，其中A(l) = Na， K, Rb， Cs和E = Se, Te。通过与碘或溴氧化，SeCx聚合物应该是可获得的，因此有望提高导电性，并且可能在光电子学领域引起兴趣。同样，基于芳香双（乙烯基硒酸盐）的配位聚合物也有望具有高导电性，我们也希望在提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，从而有望在光电子学领域等有趣的应用中得到应用。除了计划中的合成和分析，该项目还包括对单个分子片段和扩展固体的量子力学计算。

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.