Supramolecular Photochemistry: Guest-Host Complexes and Supermolecules

9313102特罗将研究超分子系统的光化学行为，特别是客体-宿主络合物和超分子。客体体系包括生成三重态双酯自由基对的前体酮，以及作为电子给体受体转移对的金属络合物。主体体系包括胶体胶束聚集体、双螺旋DNA和多孔分子晶体沸石。这些超分子包括由大环环酮光解产生的双自由基和由DNA间隔物在空间中以固定距离分隔的供体-受体络合物。这项研究的目标包括发现新的知识，从而能够控制涉及双自由基和胶束自由基对等高活性物种的超分子体系的化学，以及金属络合物之间的光诱导电子转移过程。来自有机动力学项目的这笔赠款支持哥伦比亚大学尼古拉斯·J·特罗教授的继续工作。超分子化学被定义为超越分子的化学。我们将研究两类重要的超分子：客体络合物和超分子。客体-宿主复合体由两个或更多分子组成，这些分子通过引力而不是化学键结合在一起。要研究的超分子可以看作是由两个或两个以上的亚基组成的，由间隔基团连接。这些超分子的结构和动力学以及光解产生的活性中间体将被研究。这项研究的结果将被应用于涉及界面化学的技术活动，具有不寻常性质的材料的表征，以及理解小客体分子与生物分子的结合。***

9313102 Turro The photochemical behavior of supramolecular systems will be studied, in particular guest-host complexes and supermolecules. The guest systems include precursor ketones which produce triplet geminate radical pairs and metal complexes that serve as electron donor acceptor transfer pairs. The host systems include colloidal micellar aggregates, double helical DNA and porous molecular crystalline zeolites. The supermolecules include biradicals produced by photolysis of large ring cyclic ketones and donor-acceptor complexes separated in space at fixed distances by a DNA spacer. The objectives of the proposed research include the discovery of new knowledge which will allow the control of the chemistry of supramolecular systems that involve highly reactive species such as biradicals and micellized radical pairs, and the photoinduced electron transfer processes between metal complexes. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Nicholas J. Turro at Columbia University. Supramolecular chemistry has been defined as the chemistry beyond the molecule. Two important classes of supramolecules will be studied: guest-host complexes and supermolecules. Guest-host complexes consist of two or more molecules that are held together by attractive forces, rather than chemical bonds. The supermolecules to be studied can be viewed as a consisting of two or more subunits, connected by spacer units. The structure and dynamics of these supramolecules as well as reactive intermediates that will generated by photolysis will be studied. The results of this study will find applications to technological activities involving chemistry at interfaces, the characterization of materials possessing unusual properties, and to an understanding of the binding of small guest molecules to biomolecules. ***