University of Catania, Dipartimento di Scienze Chimiche, Catania, Italy.
Chem Commun (Camb). 2012 Aug 25;48(66):8165-76. doi: 10.1039/c2cc31856c. Epub 2012 Jun 12.
Self-organization is the driving force that led to the evolution of life. Rationalization of the spontaneous self-assembly paradigm will offer tremendous potentialities to obtain a wide variety of complex systems, having specific functionality and properties. Herein, we will propose an overview of the developments in non-covalent syntheses of multi-porphyrin supramolecular species in aqueous solution. This work took inspiration from the pioneering studies aimed at rationalizing the spontaneous aggregation processes, governed by conventional solution properties (i.e. pH, ionic strength, and concentration). The more recent chemical strategies, to hierarchically manipulate the cooperative nature of weak interactions to design and synthesize supramolecular entities having pre-determined structure and properties, demonstrate the feasibility to attain, in a reproducible manner, molecular organization to supramolecular levels. In particular, calixarene-porphyrin species represents concrete evidence of a quantitative complexation, governed by precise hierarchical rules, which together with a rational functionalization of the molecular components leads to supramolecular entities of well-defined and tunable stoichiometry. These systems, thus, represent fertile ground to envisage and implement controlled self-organization strategies as bottom up methodologies to obtain supramolecular nanostructures and smart nanomachines.
自组织是导致生命进化的驱动力。自发自组装范式的合理化将为获得具有特定功能和特性的各种复杂系统提供巨大的潜力。在此，我们将对水溶液中多卟啉超分子物种的非共价合成的发展进行概述。这项工作的灵感来自于旨在合理化自发聚集过程的开创性研究，这些过程受常规溶液性质（即 pH 值、离子强度和浓度）的控制。最近的化学策略，用于分层操纵弱相互作用的协同性质以设计和合成具有预定结构和性质的超分子实体，证明了以可重复的方式实现从分子组织到超分子水平的分子组织的可行性。特别是杯芳烃-卟啉类物质代表了定量络合的具体证据，这种络合受精确的分层规则控制，与分子组件的合理功能化相结合，导致具有明确定义和可调化学计量比的超分子实体。这些系统因此为设想和实施受控自组织策略提供了肥沃的土壤，这些策略是作为自下而上的方法来获得超分子纳米结构和智能纳米机器。
