Organophosphorus Avenues Toward Molecular and Supramolecular Sustainable-Energy Materials

拟议的研究计划的首要主题是新型有机磷材料的设计，合成和表征。更具体地说，该研究针对几个以能源为重点的主题，通过自下而上的合成方法解决能源的有效和可持续使用，转换和/或储存。到目前为止，我的团队已经能够建立有机磷物种作为独特和强大的先进功能材料，具有非常理想的性能（强和可调的发光，电子受体功能，特别是稳定的氧化还原化学），使我们的分子构建块上级候选人的各种重要的可持续能源应用。我们现在正处于一个十字路口，使我们能够以一种新颖的、颠覆性的研究方法，在能源转换和储存方面进入一个基本上未知的领域。在分子尺度上，该提案的目标是合成新型电子活性结构单元，并建立关键的结构-性能关系。第二个目标是纳米/微观尺度，以解决新型有机能源材料的下一个挑战-高度有序的体相。在实际应用中，需要整体材料来显示最佳的电子通信，并且已经确定高度有序的系统能够在这方面表现出色。利用目标分子构建块，自组装特征将被安装在材料内以产生高度有序的纳米/微观体相，其以液晶和凝胶的形式，当与溶液中的孤立分子相比时，预期显示出增强的电子特征。这同样适用于将新的结构单元作为整体组分引入共辄聚合物的主链内，或作为适当改性的聚苯乙烯的侧链官能化。此外，能量也可以有效地储存在化学键中，特别是在可以作为传统碳氢化合物燃料或非传统燃料的物质中，这是太阳能燃料背后的主要概念。该计划中的第三个流针对过渡金属基催化剂，将水或二氧化碳等基质转化为可燃燃料（分别用于燃料电池或传统内燃机）。具体来说，我们的目标是新型催化剂，这些催化剂具有独特的有机磷基配体组，以稳定水和二氧化碳转化过程中的活性中间体。由于其多学科性质，拟议的研究计划涵盖了有机材料化学的全部范围，包括先进的合成，建模，广泛的表征和应用。拟议研究的目标应用涉及新的能源和环境技术，这些技术要么减少能源的使用，要么通过转换太阳能发电构成可持续的途径。为了提供一种通过太阳能转换（或传统的碳氢化合物燃料）获得的能量储存手段，该研究计划还针对能够储存电荷的新型有机电池材料的开发，再次使用有机磷构建块和自组装方法。此外，太阳能燃料催化剂的有针对性的发展允许使用水和/或二氧化碳作为底物以化学键的形式储存能量。因此，该计划将提供关键的知识，并将加拿大战略性地置于为我们星球的可持续未来开发基本技术的最前沿。

The overarching theme of the proposed research program is the design, synthesis and characterization of novel organophosphorus materials. More specifically, the research targets several energy-focused topics, addressing the efficient and sustainable use, conversion, and/or storage of energy via a synthetic bottom-up approach. To date my group has been able to establish organophosphorus species as unique and powerful advanced functional materials with highly desirable properties (strong and tunable luminescence, electron-acceptor features, and stable redox chemistry in particular) that make our molecular building blocks superior candidates for a variety of important sustainable energy applications. We are now at a crossroads that allows us to venture into largely uncharted territory with regard to the conversion and storage of energy in a novel, disruptive research approach. On the molecular scale, the proposal targets the synthesis of novel electronically active building blocks and establishing crucial structure-property relationships. A second stream targets the nano/microscopic scale to address the next challenge for novel organic energy materials – highly ordered bulk phases. In practical applications, an ensemble of bulk materials is required to show optimum electronic communication, and it has been established that highly ordered systems are capable of performing superbly in this regard. Utilizing the targeted molecular building blocks, self-assembly features will be installed within the materials to generate highly ordered nano/microscopic bulk phases in the form of liquid crystals and gels that are expected to show enhanced electronic features, when compared to isolated molecules in solution. The same applies to the incorporation of the new building blocks as integral components within the backbone of conjugated polymers, or as side chain functionalization of suitably modified polystyrenes. Moreover, energy can also be efficiently stored in chemical bonds, particularly in species that can then act as conventional hydrocarbon fuels or non-conventional fuels, which is the main concept behind solar fuels. The third stream in the program targets transition metal-based catalysts that convert substrates, such as water or carbon dioxide, into combustible fuels (for fuel cells, or traditional combustion engines, respectively). Specifically we are targeting novel catalysts that bear unique, organophosphorus-based ligand sets to stabilize reactive intermediates in the conversion of water and carbon dioxide. Due to its multidisciplinary nature, the proposed research program covers the full breadth of organic materials chemistry encompassing advanced synthesis, modeling, extensive characterization, and application. The applications targeted by the proposed research involve novel energy and environment technologies that either reduce the use of energy, or constitute sustainable avenues toward producing electricity by converting solar power. To provide for a means of storing energy, obtained either via solar energy conversion (or traditional hydrocarbon fuels), this research program also targets the development of novel organic battery materials that are capable of storing charges, again using an organophosphorus building-block and self-assembly approach. Moreover, the targeted development of solar fuel catalysts allows storing energy in the form of chemical bonds using water and/or carbon dioxide as substrate. This program will thus provide crucial knowledge and strategically position Canada at the forefront of the development of essential technologies for a sustainable future of our planet.