The chemistry of metal-diselenolene complexes

金属-二硫杂环戊烯配合物的配体非无辜性和可逆氧化还原行为的组合导致独特的电、光、磁和导电性质。由于这些性质，含二硫杂环戊烯的配合物已被研究用于乏核燃料的分配，聚合物生产中烯烃的纯化，染料敏化太阳能电池，H2O光分解催化剂，磁性材料，化学微传感器，光限幅装置以及最近的癌症治疗。因此，鉴于二硫杂环戊烯络合物的丰富和多样的化学性质，它们仍然是高度关注的主题并不奇怪。虽然过去的研究表明二硒烯和二硫烯配合物在化学上有相似之处，但也存在显着差异，这需要对二硒烯配合物进行进一步的研究。然而，二硒烯络合物还没有得到很好的研究，无论是实验还是理论。事实上，在ISI知识网上快速搜索“二硒代戊烯”会得到38个结果，而搜索“二硫代戊烯”会得到1,347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，使用计算工具的组合，这些二硒烯配合物在生物无机化学以及材料科学中的作用将进行调查。特别是，密度泛函理论（DFT）将被用来研究的结构，还原电位和HOMO-LUMO间隙能量的二硒烯配合物。利用含时密度泛函理论研究了二硒烯配合物的光化学性质。值得注意的是，已经研究了混合配体二亚胺-金属-二硫杂环戊烯络合物用于染料敏化太阳能电池和用于H2O的光分解以形成H2。关于含二硫纶的酶系统的仿生二硒纶类似物将使用组合的量子力学/分子力学（QM/MM）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，随着化石燃料的耗尽，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，二氧化碳的产生也在继续。因此，设计用于封存CO2的新催化剂对我们的未来也至关重要。重要的是，从这项研究计划中获得的知识将提供对二硒烯络合物化学的深入了解，这将导致设计用于染料敏化太阳能电池的新的含二硒烯的组件，烯烃纯化催化剂，通过光催化分解水和催化还原CO2到甲酸盐的可再生生产H2的催化剂。

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.**