Development of Molybdenum and Tungsten Cluster Complexes for Singlet Oxygen Generation and Biological Implications

含[{M6 I8} L 6]2-簇合物（M = Mo，W）和六个末端配体（L）的金属碘化物配合物由于其固有的电子物理性质，在发光器件、染料敏化太阳能电池、光学氧传感器和敏化剂等方面具有广泛的应用前景，引起了人们的极大兴趣。本项目中我们与德国和俄罗斯联合体的研究将涉及基于八面体[M6 I8]簇核（M = Mo，W）的簇合物的制备和改性，包括开发新的碘化钨簇合物，如[M5 I8]四方锥簇合物核、[M5 M 'I8]混合金属簇合物和带有帽状非金属原子（C）的[M5 I8 C]簇合物。配体（L）取代反应在我们的研究小组中对于八面体[{M6 I8}I6]2-簇合物是公认的，以产生具有[{M6 I8} L 6]2-簇合物的化合物，包括具有混合配体的偏离物。化合物的制备和光化学研究，以更深入地了解这些材料的性质，强调光致发光，和单线态氧形成下的发光猝灭。稳定的钼和钨簇化合物，能够在固态和溶液中产生单线态氧的发展被认为是重要的，因为它涉及一个杰出的潜在的化合物正在考虑中，有用的生物学意义，但也为其他利益。具有部分高化学稳定性（取决于配体的类型）的簇合物化合物的性质及其可验证的发光和单线态氧产生的异常高量子产率的潜力是异常的，因此不仅在制备化学中而且在光谱学、物理学和生物学的某些领域中是一个挑战。此类化合物的建立对于未来的卫生应用可能是独一无二的，因为它们能够在各种介质（固体、溶液和基质）中在可见光照射条件下产生单线态氧。为了实现这一目标，并对这些化合物进行更深入的理论理解，我们开发和优化了簇合物，并根据几个标准调整了它们的性质，例如在不同介质中的溶解度和化学稳定性，光化学稳定性和单线态氧量子产率。我们将制备水溶性簇，固定到或表面上的矩阵，研究生物物理性质，并调查其在生物环境中的活性，这意味着固定化的簇化合物的生物相容性矩阵是重要的。在这些研究的过程中，我们将确定，分析和了解有关的外部先决条件的簇化合物，（簇O2）的能量转移条件高单线态氧的产生。

Due to their intrinsic photophysical properties, metal iodide complexes containing [{M6I8}L6]2- clusters with M = Mo, W and six terminal ligands (L) have attracted considerable interest for their prospective applications as light-emitting devices, dye-sensitized solar cells, optical oxygen sensors, and sensitizers. Studies of our joint German-Russian consortium within this project will involve the preparation and modification of cluster compounds based on the octahedral [M6I8] cluster core with M = Mo, W, including the development of new tungsten iodide clusters, such as [M5I8] square pyramidal cluster core, [M5M´I8] mixed metal clusters, and [M5I8C] clusters with a capping non-metal atom (C). Ligand (L) substitution reactions are well-established in our research groups for octahedral [{M6I8}I6]2- clusters, to yield compounds with [{M6I8}L6]2- clusters including deviates with mixed ligands. Compounds are prepared and studied photochemically to get a deeper understanding regarding the properties of these materials emphasizing photoluminescence, and luminescence quenching under formation of singlet oxygen. The development of stable Mo and W clusters compounds, capable for singlet oxygen generation in solid state and in solution is considered important because it involves a distinguished potential of compounds under consideration, useful in biological implications but also for other benefit. The properties of cluster compounds, with in part high chemical stability (depending on the type of ligand) and their verifiable potential of exceptional high quantum yields for luminescence and singlet oxygen generation is exceptional and thus a challenge not only in preparative chemistry but also in some fields of spectroscopy, physics, and biology. The establishment of such compounds may be unique for future applications in hygiene, due to their capability of singlet oxygen generation under visuals light irradiation condition in various media (solid, solution, and in matrices). For this goal and for a deeper theoretical understanding of such compounds we develop and optimize cluster compounds and tune their properties related to several criteria, such as solubility and chemical stability in different media, photochemical stability and singlet oxygen quantum yields. We will prepare water soluble clusters, immobilized into, or on the surface of matrices, study photophysical properties, and investigate their activity in biological environments, meaning that an immobilization of cluster compounds on biocompatible matrices is important. In course of these studies we will determine, analyze and learn about external preconditions of cluster compounds, related to the (cluster to O2) energy transfer conditions for high singlet oxygen generation.