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Energy‐Efficient Iodine Uptake by a Molecular Host⋅Guest Crystal

Xue Yang, Chunyang Li, Michel Giorgi, Didier Siri, Xavier Bugaut, Bastien Châtelet, Didier Gigmès, Mehdi Yemloul, Virginie Hornebecq, Anthony Kermagoret, Sophie Brasselet, Alexandre Martinez, David Bardelang

2022Angewandte Chemie International Edition25 citationsDOIOpen Access PDF

Abstract

Abstract Recently, porous organic crystals (POC) based on macrocycles have shown exceptional sorption and separation properties. Yet, the impact of guest presence inside a macrocycle prior to adsorption has not been studied. Here we show that the inclusion of trimethoxybenzyl‐azaphosphatrane in the macrocycle cucurbit[8]uril (CB[8]) affords molecular porous host⋅guest crystals ( PHGC‐1 ) with radically new properties. Unactivated hydrated PHGC‐1 adsorbed iodine spontaneously and selectively at room temperature and atmospheric pressure. The absence of (i) heat for material synthesis, (ii) moisture sensitivity, and (iii) energy‐intensive steps for pore activation are attractive attributes for decreasing the energy costs. 1 H NMR and DOSY were instrumental for monitoring the H 2 O/I 2 exchange. PHGC‐1 crystals are non‐centrosymmetric and I 2 ‐doped crystals showed markedly different second harmonic generation (SHG), which suggests that iodine doping could be used to modulate the non‐linear optical properties of porous organic crystals.

Topics & Concepts

SorptionAdsorptionIodineCrystal (programming language)PorosityMoleculeDopingActivation energyChemistryChemical engineeringMaterials scienceChemical physicsPhysical chemistryOrganic chemistryOptoelectronicsEngineeringComputer scienceProgramming languageCovalent Organic Framework ApplicationsMetal-Organic Frameworks: Synthesis and ApplicationsSupramolecular Chemistry and Complexes