Macromolecular, Supramolecular and/or Nanomolecular Photophysics and Photochemistry of d10 and d8 Complexes

在这个由大分子、超分子和纳米化学项目资助的项目中，北德克萨斯大学（UNT）的Mohammad Omary正在开发一组新的化合物，用于替代能源技术的催化剂。这些化合物的作用是加速水分解为氢和氧的速度，释放出曾经在每个水分子中将氢原子和氧原子结合在一起的能量。在这个项目中开发的化合物预计比现有使用的材料具有更大的稳定性，从而扩大了这种有前途的新替代能源的实用性。该项目正在加强UNT与其他美国大学，国家实验室和私营部门实体之间的一些现有的学术/政府/工业合作，以及一些现有的和新的国际合作。通过开发有前途的新技术，这项研究正在对能源相关科学产生更广泛的影响。在这个项目中，一系列具有不同分子和纳米结构复杂性的磷光配合物正在研究它们作为水分解光催化剂的潜在用途。基于金属有机成分的新型光催化剂候选物正在开发中，以在存在水和阳光的实际环境下产生更大的材料稳定性。该项目的重点是设计一种新的实用的多电子光催化剂候选物，可以在水而不是有机或有机/水混合介质中工作。其目的是利用均匀或非均匀作用于固体膜的催化剂，以高效、环保的方式分解水，以增加坚固性，浓缩活性物质，并利用分子间相互作用来潜在地敏感协同电子转移。在保持高发光量子产率和长磷光寿命的同时，水溶性是外球多电子光催化非常理想的特性。Omary小组在本项目中开发的大分子、超分子和纳米分子复合物的多个实施方案满足了这些条件，以努力提高当前水分解光敏剂的技术水平。对于内球过程，单核和多核配合物被设计为在某些溶液组合物中充当6-12个光电子的能量储存器，而一些固体光催化剂具有提供几乎无限电子储存器的潜力。这些假设正在通过检查具有10或8个价电子的配合物的光物理、光化学和电化学性质作为溶液浓度或薄膜掺杂与结晶固体状态的函数来评估。

In this project funded by the Macromolecular, Supramolecular and Nanochemistry program, Mohammad Omary of the University of North Texas (UNT) is developing a new group of compounds for use as catalysts in alternative energy technologies. The compounds serve to accelerate the rate at which water is decomposed to hydrogen and oxygen, releasing the energy that once held the hydrogen and oxygen atoms together in each water molecule. The compounds being developed in this project are expected to have greater stability than existing materials in use, thus extending the practicality of this promising new source of alternative energy. The project is strengthening several existing academic/government/industrial collaborations between UNT and other US universities, national laboratories, and private sector entities as well as some existing and new international collaborations. The research is having a broader impact on energy-related science through the development of promising new technologies.In this project, a series of phosphorescent complexes with various molecular- and nano-structural complexity are being investigated for their potential use as photocatalysts for water splitting. New photocatalyst candidates based on metal-organic compositions are being developed to engender greater material stability under practical environments in the presence of water and sunlight. The project focuses on a new design of practical multi-electron photocatalyst candidates that can operate in an aqueous instead of organic or mixed organic/aqueous media. The intent is to target water splitting in an efficient, environmentally-responsible manner using catalysts that operate homogeneously, or heterogeneously via solid films in order to increase ruggedness, concentrate the active material, and utilize intermolecular interactions to potentially sensitize cooperative electron transfer. Water solubility, while maintaining high luminescence quantum yield and long phosphorescence lifetime, is a highly desirable attribute for outer-sphere multi-electron photocatalysis. These conditions are satisfied by multiple embodiments of the macromolecular, supramolecular, and nanomolecular complexes that the Omary group is developing in this project in an effort to improve the state of the art of current water splitting photosensitizers. For inner-sphere processes, mono- and multi-nuclear complexes are designed to act as energy reservoirs for 6-12 photoelectrons in some solution compositions, whereas some solid photocatalysts have the potential to provide an almost infinite reservoir of electrons. These hypotheses are being assessed by examining the photophysical, photochemical, and electrochemical properties of complexes possessing ten or eight valence electrons as a function of concentration in solution or doping in thin films vs. the crystalline solid state.