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

Xue Yang (1) , Chunyang Li (2) , Michel Giorgi (3) , Didier Siri (1) , Xavier Bugaut (4) , Bastien Chatelet (2) , Didier Gigmes (1) , Mehdi Yemloul (2) , Virginie Hornebecq (5, 3, 6) , Anthony Kermagoret (1) , Sophie Brasselet (7, 8) , Alexandre Martinez (2) , David Bardelang (1)

1 ICR - Institut de Chimie Radicalaire
2 ISM2 - Institut des Sciences Moléculaires de Marseille
3 AMU - Aix Marseille Université
4 UNISTRA - Université de Strasbourg
5 MADIREL - Matériaux divisés, interfaces, réactivité, électrochimie
6 CNRS - Centre National de la Recherche Scientifique
7 MOSAIC - MOSAIC
8 FRESNEL - Institut FRESNEL

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.

Domains: Chemical Sciences

Xue Yang, Chunyang Li, Michel Giorgi, Didier Siri, Xavier Bugaut, et al.. Energy‐Efficient Iodine Uptake by a Molecular Host⋅Guest Crystal. Angewandte Chemie International Edition, 2022, ⟨10.1002/anie.202214039⟩. ⟨hal-03871347⟩