Supramolecular Materials from Liquid Crystalline Phthalocyanines

先前NSF支持的研究已经产生了几种有效的方法来将自组织的两亲性单体分散在各种溶致中间相中，包括层状相、双连续立方相和倒置六方相。 这些研究为八取代酞菁（Pc）高度有序的柱状组装体形成超分子材料的研究提供了背景。 原型Pc 1的有序阵列（即2，3，9，10，16，17，23，24-八-（（2-苄氧基）乙氧基）酞菁铜（II））之间的强π-π相互作用控制Pc的相和表面行为。 类似于1的有序分散的柱状Pc晶胞将用于产生一维棒状聚合物，以及通过增强八取代Pc的自组装特性来产生纳米尺度上限定尺寸的自立式或表面结合的自组装Pc聚集体。 自组装的Pc聚集体可以由单个Pc或交替的Pc对组成，在相同的意义上作为交替共聚物。 这些目标将追求的octasubstituted Pc的制备和表征，将特定的自组装部分，以促进形成柱状阵列的交替对Pc。 此外，将制备由三个类似于Pc 1的亚基组成的不对称Pc，第四个亚基具有连接的无规卷曲寡聚体。 吸引性N-N相互作用和排斥性卷曲-卷曲相互作用之间的平衡预期控制这些盘-卷曲低聚物的聚集。 这些新纳米材料的合成和分子表征研究将通过合作分析研究得到补充。%超分子材料可以通过设计分子实体来产生，所述分子实体在纳米到微米尺度上自组装和/或自组织成非共价缔合的集合体。 这些材料的组织性质为生物和材料科学中的应用提供了几个有吸引力的特征，例如催化，分离，表面改性，治疗，诊断，信号转导等。

Prior NSF supported research has led to several effective methods to polymerize self-organized amphiphilic monomers in a variety of lyotropic mesophases including lamellar, bicontinuous cubic, and inverted hexagonal phases. These studies provide the background for the proposed research into the formation of supramolecular materials from highly ordered columnar assemblies of octasubstituted phthalocyanines (Pc). Strong pi-pi interactions betweeen ordered arrays of the prototype Pc 1, i.e. 2, 3, 9, 10, 16, 17, 23, 24-octakis-((2-benzyloxy)ethoxy) phthlocyaninato Cu(II), control the phase and surface behavior of the Pc. The well ordered discotic columnar unit cells of Pc's similar to 1 will be used to create one-dimensional rod-like polymers, as well as create free standing or surface bound self-assembled Pc aggregates of defined size on the nano scale by enhancing the self-assembly characteristics of octasubstituted Pc. The self-assembled Pc aggregates may be composed of a single Pc or alternating pairs of Pc, in the same sense as alternating copolymers. These goals will be pursued by the preparation and characterization of octasubstituted Pc that incorporate specific self-assembly moieties to facilitate the formation of columnar arrays of alternating pairs of Pc. In addition unsymmetrical Pc will be prepared that are composed of three subunits similar to Pc1 with the fourth having an attached random coil oligomer. The balance between the attractive N-N interactions and the repulsive coil-coil interactions is expected to control the aggregation of these disc-coil oligomers. The synthesis and molecular characterization studies on these new nanomaterials will be complemented by collaborative analytical studies.%%%Supramolecular materials can be created by the design of molecular entities that self-assemble and/or self-organize into non-covalently associated ensembles on the nano to micro scale. The organized nature of these materials offer several attractive features for applications in both biological and materials sciences, e.g. catalysis, separations, surface modification, therapeutics, diagnosis, signal transduction, among others.