Discovery-based dye chemistry: synthesis and properties of new functional molecules, ligands, and coordination complexes

几千年来，有机染料和颜料一直被用于为我们的世界着色（纺织品、油漆、涂料等），最初使用天然染料，但现在主要使用合成染料。有色分子还可以具有其他能力，如氧化还原活性、发射、光化学活性或与金属结合的能力。这些特性使它们在催化太阳能转换以及健康和医学等广泛应用中非常有用。许多研究小组的重点是为特定应用优化特定类型的已知染料。这个优化过程包括合成染料/络合物的几个相关衍生物（通常通过改变取代基）和发展结构-性质关系。我们小组的方法本质上更基本。我们的目标是设计、制造、研究和开发新型染料及其金属配合物。我们想让新分子具有有趣/创新/有用的特性（例如光物理、氧化还原）。我们的长期目标是为上述应用领域的其他研究人员扩大分子工具包。我们对可见光谱和近红外光谱低端的强光吸收分子特别感兴趣。这个光谱区域对于许多研究领域都是至关重要的，但要使新的发色团吸收这里的光是具有挑战性的。这一建议的部分重点是我们最近成功地将著名的纺织颜料靛蓝转化为更可溶性的二亚胺类似物。本提案当前/未来的目标领域将包括：(1)通过合成和表征新的Nindigo配体衍生物和新金属，进一步探索Nindigo配合物的氧化还原/光学性质；(2) Nindigo配合物作为电子和质子储层的反应性研究；(3)针对新的ninigo结构类型开展合成探索性工作，以期发现制备近红外吸收分子和配合物的新途径。该提案的第二个重点是确定新型染料配体结构，这种结构将与金属结合，并具有极其不寻常的光学特性，即吸收高能（近红外光）。该应用程序提出了几种由杂环构建块（如吡咯，吲哚和咔唑）构建的三叉，pi扩展变体；所提出的配体系统被设计成具有极低的能量（近红外）吸收（作为自由分子和与金属结合），同时使用取代基来保持稳定性。该领域的子项目将涉及有机/杂环合成，以及合成配位化学以及上述表征方法。

Organic dyes and pigments have been used to colour our world (textiles, paints, coatings, etc) for millennia, originally using naturally occurring dyes but now mostly using dyes made synthetically. Coloured molecules can also possess other capabilities such as redox activity, emission, photochemical activity, or the ability to bind to metals. These properties make them useful in a huge range of applications including catalysis solar energy conversion, and health & medicine. A focus of many research groups is to optimize a particular known type of dye for a particular application. This optimization process involves the synthesis of several related derivatives of the dye/complex (typically by changing substituents) and developing structure-property relationships. My group's approach is more fundamental in nature. We aim to design, make, study, and develop new kinds of dyes and metal complexes thereof. We want to make new molecules have properties (e.g. photophysical, redox) that are interesting/innovative/useful. Our long term goals are to broaden the molecular toolkit for other researchers in the application-oriented areas mentioned above. We are particularly interested in molecules that are intense light absorbers at the low end of the visible spectrum and the near-infrared. This spectral region is critical for several fields of research but it is challenging to make new chromophores absorb light here. Part of this proposal focuses on our recent success in converting the famous textile pigment indigo into more soluble diimine analogues. Current/future target areas in this proposal will include (1) further exploration of the redox/optical properties of Nindigo complexes, through the synthesis and characterization of new Nindigo ligand derivatives as well as new metals; (2) reactivity studies of Nindigo complexes as electron and proton reservoirs; and (3) synthetic exploratory work targeting new Nindigo structure types, with a view to uncovering new ways to make near-infrared absorbing molecules and complexes. A second thrust of this proposal identifies new types of dye ligand structures that will bind to metals and possess extremely unusual optical properties, namely absorption of very energy (near infrared) light.  This application proposes several tridentate, pi expanded variants that are constructed from heterocyclic building blocks such as pyrroles, indoles, and carbazoles; the proposed ligand pi systems are designed to lead to exceptionally low energy (near IR) absorption (both as free molecules and bound to metals) while using substituents to maintain stability. The sub-projects in this area will involve organic/heterocyclic synthesis, as well as synthetic coordination chemistry along with the characterization methods listed above.