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

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. 1H NMR and DOSY were instrumental for monitoring the H2O/I2 exchange. PHGC‐1 crystals are non‐centrosymmetric and I2‐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.

Controlled oligomeric guest stacking by cucurbiturils in water

“…After the seminal discovery of cucurbit[n]urils (CB[n], n = 5-8, 10, 13-15), 1,2 a flourishing field started to emerge, reporting many new supramolecular complexes, some of which featured by unique properties in catalysis, drug transport or crystal engineering, [3][4][5][6] and stimuli-responsive molecular shuttles. [7][8][9] In parallel, controlling the level of compound oligomerization appeared challenging but supramolecular methods afforded interesting results in this prospect.…”