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                <title level="j">Angewandte Chemie International Edition</title>
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                  <biblScope unit="volume">61</biblScope>
                  <biblScope unit="issue">49</biblScope>
                  <biblScope unit="pp">e202214039</biblScope>
                  <date type="datePub">2022-12-05</date>
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                <term xml:lang="en">Cucurbituril</term>
                <term xml:lang="en">Iodine Adsorption</term>
                <term xml:lang="en">Porous Material</term>
                <term xml:lang="en">Supramolecular</term>
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              <p>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.</p>
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