The chemistry of metal-diselenolene complexes

金属-二硫烯配合物的配体非清白性和可逆氧化还原行为的结合，产生了独特的电学、光学、磁性和导电性。由于这些性质，含二噻吩的配合物已被研究用于核废料的分解、聚合物生产中烯烃的纯化、染料敏化太阳能电池、水的光分裂催化剂、磁性材料、化学微传感器、光学限制装置，以及最近的癌症治疗。因此，鉴于二硫代烯复合物的丰富和多样的化学性质，它们仍然是一个高度感兴趣的主题就不足为奇了。虽然过去的研究表明二烯烯和二硫代烯配合物的化学性质相似，但也存在显著差异，值得对二烯烯配合物进行进一步研究。然而，二烯烯复合物在实验和理论上都没有得到很好的研究。事实上，在ISI知识网络上快速搜索“二硫烯”会产生38个结果，而搜索“二硫烯”会产生1347个结果。然而，自20世纪70年代以来，对这种含硒配体的研究一直很活跃。***因此，将使用计算工具的组合来研究这些二烯烯配合物在生物无机化学和材料科学中的作用。特别是，密度泛函理论（DFT）将用于研究二烯烯配合物的结构、还原势和HOMO-LUMO间隙能。使用时间依赖的DFT将检查二烯烯配合物的光化学。值得注意的是，混合配体二亚胺-金属-二噻吩配合物已被研究用于染料敏化太阳能电池和水的光分裂形成H2。对于含二硫代烯的酶系统，仿生二烯类似物将使用量子力学/分子力学（QM/MM）相结合的方法进行研究。将进行自然成键轨道（NBO）分析，以更深入地了解用Se取代S对系统电子学的影响。值得注意的是，随着化石燃料的消耗，设计能够将太阳能转化为电能或化学能的新化合物变得更加重要。此外，由于化石燃料的持续燃烧，二氧化碳的产生仍在继续。因此，设计用于二氧化碳封存的新型催化剂对我们的未来也至关重要。重要的是，从该研究项目中获得的知识将提供对二烯烯配合物化学的深入了解，这将导致设计新的含二烯烯的成分，用于染料敏化太阳能电池，烯烃净化催化剂，通过光催化分解水和催化还原二氧化碳生成甲酸的可再生H2催化剂

The combination of ligand non-innocence and reversible redox behaviour of metal-dithiolene complexes results in unique electrical, optical, magnetic and conductive properties. Because of these properties dithiolene-containing complexes have been investigated for potential use in the partitioning of spent nuclear fuels, the purification of olefins in the production of polymers, dye-sensitized solar cells, catalysts for the photo splitting of H2O, magnetic materials, chemical microsensors, optical limiting devices, and more recently in the treatment of cancer.***Thus, given the rich and diverse chemistry of dithiolene complexes it is not surprising that they remain a subject of high interest. While past research has shown parallels in the chemistry of diselenolene and dithiolene complexes significant difference also exist which warrants further research into diselenolene complexes. However, diselenolene complexes have not been as well studied either experimentally or theoretically. Indeed, a quick search of 'diselenolene' on ISI web of knowledge generates 38 hits whereas a search for 'dithiolene' results in 1,347 hits. Yet, the search for such Se-containing ligands has been active since the 1970s.***Hence, using a combination of computational tools the role of these diselenolene complexes in bioinorganic chemistry as well as in materials science will be investigated. In particular, density functional theory (DFT) will be used to investigate the structures, reduction potentials and HOMO-LUMO gap energies of diselenolene complexes. Using time-dependent DFT the photochemistry of diselenolene complexes will be examined. Notably, mixed ligand diimine-metal-dithiolene complexes have been investigated for use in dye-sensitized solar cells and to the photo splitting of H2O to form H2. Regarding dithiolene containing enzymatic systems the biomimetic diselenolene analogues will be investigated using a combined quantum mechanics/molecular mechanics (QM/MM) approach. Natural bonding orbital (NBO) analyses will be performed to provide greater insight into the effect of substituting the S with Se on the electronics of the system.***It is noted that with the depletion of fossil fuels it becomes more important for the design of new compounds that can convert solar energy into electrical or chemical energy. Moreover, from the continued burning of fossil fuels the production of CO2 continues. Thus, the design of new catalysts to be used in the sequestration of CO2, is also critical for our future. Importantly, the knowledge gained from this research program will provide insight into chemistry of diselenolene complexes that will lead to the design of new diselenolene containing components for use in dye-sensitized solar cells, catalysts for olefin purification, catalysts for the renewable production of H2 via the photocatalytic splitting of water and the catalytic reduction of CO2 to formate.**