Arylene ethynylene macrocycles: from molecular hosts to components of high-performance supramolecular architectures

Abstract

Supramolecular chemistry of conjugated and conformationally rigid arylene ethynylene macrocycles (AEMs) has been the subject of increasing recent interest. AEMs are suited to function as supramolecular building blocks and hosts for small molecular guests thanks to their well-defined, non-collapsible central cavities and the potential for long range ordering through intermolecular π-stacking. Their syntheses are highly modular--albeit typically lengthy--allowing access to a great structural variety of AEM candidates for applications as carbon-rich mesogens and ligands in liquid crystals, nanoporous solids, molecular electronics, and chemical sensors. In this perspective, we highlight our recent work on the inclusion complexes and porous materials constructed from AEMs. Through this prism, we reflect on the recent advances and the remaining challenges in the supramolecular chemistry of AEMs.

A review of oligo(arylene ethynylene) derivatives in molecular junctions

“…1b). OAEs have found applications in diverse fields, including biosensors and biocides 1 (including recently against the SARS-CoV-2 virus 2 ), supramolecular chemistry [3][4][5] and sensors, 6,7 covalent organic frameworks, 8 organic photovoltaics, 9 and liquid crystals. 10 Synthetically, OAEs have been used as graphene nanoribbon precursors 11 and OAE templates have been used to prepare OAE macrocycles.…”

“…Other than this, the authors state that the addition of the cyclodextrin ring had "no clear effect" on molecular conductance properties. 208 In contrast, the shielding by the cyclodextrin rings in [3]rotaxane 27 was reported to afford sharp conductance features in STM-BJ experiments due to the restriction of intramolecular rotations, but features corresponding to multiple molecules in the junction were observed. 210 Neither of these studies included a direct comparison with an unshielded analogue using the same STM-BJ equipment, making it difficult to confidently discern the overall effect of rotaxane shielding on molecular conductance.…”

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

“…The development of angle-strained alkyne-containing macrocyclesh as been described in several excellent reviews. [31][32][33][34][35][36][37][38][39][40] For alkynecontaining shape-persistent macrocycles withouts train [41][42][43][44][45][46][47] and macrocyclic metal complexes, [48][49][50] refer to other reviews.…”

“…Because of the classification based on this definition, alkyne‐containing π‐conjugated macrocycles without strain (∠ sp >170°) are not included. The development of angle‐strained alkyne‐containing macrocycles has been described in several excellent reviews . For alkyne‐containing shape‐persistent macrocycles without strain and macrocyclic metal complexes, refer to other reviews.…”

Butterfly‐Like Triarylamines with High Hole Mobility and On/Off Ratio in Bottom‐Gated OFETs

“…[15] Interestingly, aryleneethynylene spacers have been investigated widely and displayed unique properties. [16,17] The alkynyl groups are beneficial to increase the rigidity of the molecular skeleton along with enhancing the charge transport through the efficient delocalization of the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LUMO). [18] For instance, Wang et al [18] designed perylene diimides (PDI) with aryleneethynylene spacer that possesses quasi-planar rigidity with increased mobility than the prototype PDI core.…”