Regulating the Structures of Self-Assembled Mechanically Interlocked Moleculecular Constructs via Dianion Precursor Substituent Effects
datasetposted on 08.04.2020, 20:31 authored by Xu-Lang Chen, Yun-Jia Shen, Chao Gao, Jian Yang, Xin Sun, Xin Zhang, Yu-Dong Yang, Gong-Ping Wei, Jun-Feng Xiang, Jonathan L. Sessler, Han-Yuan Gong
Substituent effects play critical roles in both modulating reaction chemistry and supramolecular self-assembly processes. Using substituted terephthalate dianions (p-phthalic acid dianions; PTADAs), the effect of varying the type, number, and position of the substituents was explored in terms of their ability to regulate the inherent anion complexation features of a tetracationic macrocycle, cyclo(2,6-di(1H-imidazol-1-yl)pyridine)(1,4-dimethylenebenzene) (referred to as the Texas-sized molecular box; 14+), in the form of its tetrakis-PF6– salt in DMSO. Several of the tested substituents, including 2-OH, 2,5-di(OH), 2,5-di(NH2), 2,5-di(Me), 2,5-di(Cl), 2,5-di(Br), and 2,5-di(I), were found to promote pseudorotaxane formation in contrast to what was seen for the parent PTADA system. Other derivatives of PTADA, including those with 2,3-di(OH), 2,6-di(OH), 2,5-di(OMe), 2,3,5,6-tetra(Cl), and 2,3,5,6-tetra(F) substituents, led only to so-called outside binding, where the anion interacts with 14+ on the outside of the macrocyclic cavity. The differing binding modes produced by the choice of PTADA derivative were found to regulate further supramolecular self-assembly when the reaction components included additional metal cations (M). Depending on the specific choice of PTADA derivatives and metal cations (M = Co2+, Ni2+, Zn2+, Cd2+, Gd3+, Nd3+, Eu3+, Sm3+, Tb3+), constructs involving one-dimensional polyrotaxanes, outside-type rotaxanated supramolecular organic frameworks (RSOFs), or two-dimensional metal–organic rotaxane frameworks (MORFs) could be stabilized. The presence and nature of the substituent were found to dictate which specific higher order self-assembled structure was obtained using a given cation. In the specific case of the 2,5-di(OH), 2,5-di(Cl), and 2,5-di(Br) PTADA derivatives and Eu3+, so-called MORFs with distinct fluorescence emission properties could be produced. The present work serves to illustrate how small changes in guest substitution patterns may be used to control structure well beyond the first interaction sphere.
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Self-Assembled Mechanically Interlocked Moleculecular Constructsphthalic acid dianionsOHmetal cationsfluorescence emission propertiesparent PTADA systemDianion Precursor Substituent Effects Substituent effectssupramolecular self-assembly processesorder self-assembled structureMORFanion complexation featuresoutside-type rotaxanated supramolecularmodulating reaction chemistryguest substitution patternsRSOFDMSO