The chemistry of metal-diselenolene complexes

金属-二硫杂环戊烯络合物的配位体非无害性和可逆氧化还原行为的结合使其具有独特的电、光、磁和导电性能。由于这些性质，含二硫代烯的络合物已被研究用于乏核燃料的分配、聚合物生产中的烯烃提纯、染料敏化太阳能电池、用于光分解H2O的催化剂、磁性材料、化学微传感器、光限幅器件，以及最近在癌症治疗中的应用。*因此，鉴于二硫代烯络合物丰富多样的化学特性，它们仍然是一个高度感兴趣的主题也就不足为奇了。虽然过去的研究表明二茂铁烯和二硫烯烯络合物的化学结构是相似的，但也存在着显着的差异，这就需要对二硒烯烯络合物进行进一步研究。然而，二硒烯烯类化合物的实验和理论研究都不是很好。事实上，在三军情报局的知识网络上快速搜索“二硫烯烯”会得到38个匹配结果，而搜索“二硫烯烯”会得到1347个匹配结果。然而，自20世纪70年代以来，对这类含Se配体的寻找一直很活跃。*因此，将使用一系列计算工具来研究这些二茂铁烯络合物在生物无机化学和材料科学中的作用。特别是用密度泛函理论(DFT)研究了二茂铁烯络合物的结构、还原势和HOMO-LUMO能级。用含时密度泛函理论研究了二硒烯烯络合物的光化学。值得注意的是，混合配体二亚胺-金属-二硫烯络合物已被用于染料敏化太阳能电池，并用于H2O的光解生成H2。对于含二硫代烯的酶体系，将采用量子力学/分子力学(QM/MM)相结合的方法研究仿生二硫烯烯类似物。将进行自然成键轨道分析，以便更深入地了解用Se取代S对系统电子学的影响。*注意到，随着化石燃料的枯竭，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，用于二氧化碳封存的新型催化剂的设计对我们的未来也是至关重要的。重要的是，从这项研究计划中获得的知识将有助于深入了解二硒烯化合物的化学，这将导致设计用于染料敏化太阳能电池的新的二烯烯化合物成分、用于烯烃净化的催化剂、用于通过光催化分解水来可再生生产氢气的催化剂以及催化还原二氧化碳生成甲酸盐的催化剂。

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.**