Host-Guest Complexation: A Modular Approach for Structural Control (MAS-Control) in Supramolecular Polymerization

在有机软材料中实现增强功能效率的关键原则通常依赖于通过定义和规定其大小和分散性来调节结构及其受控组织的机制。在解决相关重大挑战的同时，超分子化学家已经掌握了在动力学条件下工程分子自组装过程的艺术，无论是通过引入单体分子结构的构象变化还是通过非成核过程。现有的报告仅限于单体的特定分子结构，这就需要探索可编程的聚合物结构，以推进超分子化学领域。本提案的主要目标是开发一种适用于任何分子设计的超分子聚合物结构控制的通用和模块化设计策略。首先，该方案旨在通过单体构建块的主客体超分子络合，在动力学剖面中实现高可编程性，以创建一个动力学捕获状态。下一步，将利用外部刺激引发的单体构建模块的主客体分解来实现动态控制的生长过程。此外，通过调节外部刺激的程度，超分子聚合物体系将具有可编程的结构组织。因此，实现这一目标是解决现有结构控制挑战的关键，本文提出的“主客体化学模块化和通用方法”对分子自组装过程进行编程，控制其大小和分散性是非常合适的。这项计划中的研究将是一个范式的转变，并将在一系列实现软功能材料的新概念和主题方面培养下一代科学家、技术专家和创新者。

Key principles to attain enhanced functional efficiency among organic soft materials often rely on mechanisms regulating structures and their controlled organization by defining and dictating their size and dispersity. While addressing the associated grand challenges, supramolecular chemists have mastered the art of engineering molecular self-assembly process under kinetic conditions, either by virtue of introduced conformational changes in the molecular structures of the monomers or via the off-nucleation process. The available reports are limited to specific molecular structures of the monomers, and this necessitates exploration of programmable polymeric structures to advance the field of supramolecular chemistry. The major objective of this proposal is to develop a universal and modular design strategy for structural control in supramolecular polymers, applicable to any molecular design. The proposal aims at achieving high programmability in the kinetic profiles by the host-guest supramolecular complexation of the monomer building blocks to create a kinetically trapped state, to begin with. In the next step, external stimuli-triggered host-guest decomplexation of monomer building blocks will be harnessed to enable kinetically controlled growth processes. Further, by modulating the extent of external stimulation, the supramolecular polymeric system will be advanced with the programmable structural organization. Thus, reaching this goal is the key to unravel the existing challenges of structural control, and herein proposed "host-guest chemistrya modular and universal approach" to programming molecular self-assembly process with controlled size and dispersity- is very appropriate. This planned research will be a paradigm shift and will train the next generation of scientists, technologists, and innovators in a range of new concepts, and topics for realizing soft functional materials.