Hierarchical Assemblies of Supramolecular Coordination Complexes.
Hierarchical Assemblies of Supramolecular Coordination Complexes.
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DOI：
10.1021/acs.accounts.8b00233
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发表时间：
2018-09-18
影响因子：
18.3
通讯作者：
Stang PJ
中科院分区：
文献类型：
--
作者：
Datta S;Saha ML;Stang PJ
分级自组装（HAS）是一种多层次的组织过程，其首先通过非共价相互作用将基本分子单元组装成有序的二级结构，二级结构进一步充当构建块以在下一级（一个或多个）形成更复杂的多功能超结构。HAS策略已被用作一种通用的方法，用于制备具有确定尺寸和形态、可调发光和生物重要性的软物质纳米结构。然而，如果采用良好定义的动态结构作为核心，在连接时形成所需的纳米结构，则可以大大简化这种制备。具有明确形状、尺寸和内腔的离散超分子配位化合物已被广泛用于构建具有功能多样性的分级体系。该帐户总结了近年来在制备基于SCC的HAS中使用的流行策略，并说明了如何使用动态金属配体配位与其他相互作用的组合来获得具有有趣特性的分级系统。HAS具有涉及配位驱动的自组装和氢键/主客体相互作用的双重正交相互作用，通常导致稳健和柔性的超分子凝胶。同样，SCC与合适的动态共价网络通过分级策略的杂交可用于制备具有自修复性质的材料。SCC的固有正电荷也使它们成为通过与带负电荷的生物/非生物分子的静电相互作用构建HAS的合适前体。此外，通过改变SCC的烷基/氧杂环链的数量和空间取向，HAS的亲水性和亲脂性之间的相互作用是制备有序和可调纳米结构的简单而可控的方法。某些SCC-核心的分层系统表现出可逆的多态性，通常之间的胶束，胶束和囊泡相，在响应各种外部扰动：热，光照射，pH值的变化，氧化还原活性剂等在同一时间，多个非共价相互作用介导的HAS的数量不断增长，是有前途的候选人获得功能多样的材料。基于SCC的HAS的物理化学性质已被用于许多分析应用中。例如，在金属超分子结构中嵌入基于四苯乙烯（TPE）的吡啶基配体部分限制了其苯环的分子旋转，从而赋予所得SCC微弱的发射。这种HAS在合适的溶剂中的进一步聚集导致发射强度沿着与量子产率的显著增强。他们作为敏感的传感器，不同的分析物，包括病原体，药物等HAS也是有用的开发多药系统与合作化疗效果。因此，将HAS与治疗诊断SCC结合使用细胞成像剂和化疗支架是癌症治疗诊断的有前途的药物递送策略。同时，它们对刺激的响应性，通常是由于金属-配体相互作用的动态性质，在药物释放中通过拆卸机制发挥重要作用。
Hierarchical self-assembly (HAS) is a multilevel organization process that first assembles elementary molecular units into ordered secondary structures via noncovalent interactions, which further act as the building blocks to form more complex multifunctional superstructures at the next level(s). The HAS strategy has been used as a versatile method for the preparation of soft-matter nanoarchitectures of defined size and morphologies, tunable luminescence, and biological importance. However, such preparation can be greatly simplified if well-defined dynamic structures are employed as the cores that upon linking form the desired nanoarchitectures. Discrete supramolecular coordination complexes (SCCs) with well-defined shapes, sizes, and internal cavities have been widely employed to construct hierarchical systems with functional diversity. This Account summarizes the prevailing strategies used in recent years in the preparation of SCC-based HASs and illustrates how the combination of dynamic metal–ligand coordination with other interactions was used to obtain hierarchical systems with interesting properties. HASs with dual orthogonal interactions involving coordination-driven self-assembly and hydrogen bonding/host–guest interaction generally result in robust and flexible supramolecular gels. Likewise, hybridization of SCCs with a suitable dynamic covalent network via a hierarchical strategy is useful to prepare materials with self-healing properties. The intrinsic positive charges of the SCCs also make them suitable precursors for the construction of HASs via electrostatic interactions with negatively charged biological/abiological molecules. Furthermore, the interplay between the hydrophilic and lipophilic characters of HASs by varying the number and spacial orientation of alkyl/oxyethylene chains of the SCC is a simple yet controllable approach to prepare ordered and tunable nanostructures. Certain SCC-cored hierarchical systems exhibit reversible polymorphism, typically between micellar, nanofiber, and vesicular phases, in response to various external perturbations: heat, photoirradiation, pH-variance, redox-active agents, etc. At the same time, multiple noncovalent interaction mediated HASs are growing in numbers and are promising candidates for obtaining functionally diverse materials. The photophysical properties of SCC-based HASs have been used in many analytical applications. For example, embedding tetraphenylethene (TPE)-based pyridyl ligands within metallo-supramolecular structures partially restricts the molecular rotations of its phenyl rings, endowing the resultant SCCs with weak emissions. Further aggregation of such HASs in suitable solvents results in a marked enhancement in emission intensity along with quantum yields. They act as sensitive sensors for different analytes, including pathogens, drugs, etc. HASs are also useful to develop multidrug systems with cooperative chemotherapeutic effects. Hence, the use of HASs with theranostic SCCs combining cell-imaging agents and chemotherapeutic scaffolds is a promising drug delivery strategy for cancer theranostics. At the same time, their responsiveness to stimuli, oftentimes due to the dynamic nature of the metal–ligand interactions, play an important role in drug release via a disassembly mechanism.
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