Supramolecular‐Macrocycle‐Based Crystalline Organic Materials

Abstract

macrocycles. They have been also employed to modify the surface properties of metal nanoparticles via noncovalent host−guest interactions, [31] covering their applications in drug delivery, [32] highly sensitive sensors, [33] selective catalysis, [34] and so on.In addition to their intensive applications based on their host−guest chemistry, macrocycles have also been used as building blocks to construct solid materials including porous organic polymers (POPs), [35,36] metal-organic frameworks (MOFs), [37][38][39][40][41][42][43] and crystalline organic materials (COMs). [44][45][46][47][48][49][50][51][52][53][54][55][56][57] Particular attention should be paid to COMs, a class of organic materials featuring facile preparation, high crystallinity, structural diversity, chemical stability, solution-processability, etc. [58][59][60][61][62][63][64][65][66][67][68][69][70] Different from MOFs that are composed of both inorganic (metal ions) and organic species (organic ligands) through coordination, COMs refer to a kind of crystalline materials composed of pure organics connected by either covalent or noncovalent bonds. [71][72][73] For COMs connected by noncovalent bonds, the typical materials are organic molecular crystals with intriguing properties such as semiconductor, [53] porosity, [68] etc. Owing to the inefficient packing of organic building blocks in the crystal state, some molecular crystals display extrinsic porosity, which are often termed as hydrogen-bonded organic frameworks (HOFs) [74,75] or supramolecular organic frameworks (SOFs). [76][77][78][79][80] For COMs connected by covalent bonds, typical materials are crystalline covalent organic frameworks (COFs), which were firstly reported in 2005 by Yaghi and co-workers [44] Benefitting from rigid chemical bonds and building blocks, COFs show permanent and well-ordered porosity. [45][46][47][48] Supramolecular-macrocycle-based COMs, a class of COMs with macrocycles as the main building blocks, have drawn particular attention in recent years. According to their components, supramolecular-macrocycle-based COMs can be classified into two main categories, the ones composed of pure macrocycles and the others consisting of macrocycles and other simple organic building blocks. Owing to their prefabricated cavities of a certain type, some of macrocycle-based COMs exhibit intrinsic microporosity for guest adsorption in the solid state. On the other hand, the extrinsic porosity of some macrocyclebased COMs may form due to the inefficient packing of these rigid macrocyclic molecules in the crystalline state. In certain circumstances, both intrinsic and extrinsic microporosity can be created in a single lattice of a certain COM, thus leading to Supramolecular macrocycles are well known as guest receptors in supramolecular chemistry, especially host−guest chemistry. In addition to their wide applications in host−guest chemistry and related areas, macrocycles have also been employed to construct crystalline organic materials (COMs) owing to their particular structur...

A Water-Soluble Photothermal Host–Guest Complex with pH-Sensitive Superlarge Redshift Absorption

“…It suggests that β-CD is capped on the end benzyl ring of ACAT (Figure 1b fully agreeing with the knowledge of cyclodextrin-based supramolecular chemistry in which the host-guest interaction is facilitated by hydrophobic effect and size matching. [33][34][35][36] In order to identify the stoichiometric ratio of ACAT-CD complex, the UV-Vis spectra of ACAT in the presence of β-CD with varied concentrations are summarized in Figure 1c. Accordingly, the absorbance at 530 nm which is ascribed to ACAT is dramatically increased upon the continuous addition of β-CD, accounting for the improved solubility of ACAT.…”

Synthetic Macrocycle‐Based Nonporous Adaptive Crystals for Molecular Separation

“…first described that guest species could transport through the lattice of the crystals of p ‐tert‐butylcalix[4]arene along with the single crystal‐to‐single‐crystal transformations, although the fact that there is no obvious channels/porosity in its structure [1a] . During the past five years, NACs of pillararenes have attracted considerable interest as they display great potentials for practical applications, especially in the adsorption, separation, and storage of hydrocarbons [2–20] . In 2015, Ogoshi et al.…”

“…While the properties and applications of the robust pillararenes‐based NACs are well‐established, [2b,c, 18] new NACs based on pillararene derivatives and other important synthetic macrocycles, such as biphen[3]arene, [24] leaning pillar[6]arene (i.e., leaning tower[6]arene), [25] geminiarene, [26] bowtiearene, [27] cucurbit[6]uril, [23] hybrid[3]arene, [28] and tiara[5]arene [21] have been developed and recently reported. In this Minireview, we describe some important progress in the development of synthetic macrocycles‐based NACs, especially the constructions of NACs from newly discovered macrocyclic arenes for molecular separation and vapochromic application in the last two years.…”

Cyclobutene based macrocycles

“…The concepts of supramolecular chemistry provide a natural translation of molecule constructions to create functional materials. [1][2][3] Supramolecular assemblies containing extended p-conjugated macrocycles are particularly attractive for applications in organic electronics/devices, 4,5 examples of note include cyclic porphyrins, 6,7 annulenes, 8-10 phenylenes [11][12][13][14][15] and oligothiophenes. [16][17][18] The most common building blocks of p-extended macrocycles are phenylenes, ethynylenes, thiophenes and pyrroles.…”