biostudies-literatureXu ZScience and Technology Commission of Shanghai MunicipalityPostdoctoral Science Foundation of Shanghai MunicipalityNational Natural Science Foundation of ChinaChina Postdoctoral Science FoundationShanghai Municipal Human Resources and Social Security BureauShanghaiTech UniversityZhejiang University3475-3483https://www.ebi.ac.uk/biostudies/studies/S-EPMC11423331biostudies-literatureUnknown4(9)In pursuit of environmental sustainability and energy efficiency, assorted macrocyclic compounds have recently emerged as crystalline adsorbents for the efficient molecular sieving of various chemical commodities. Herein, we delve into the conformational characteristics and solid-state packing modes of tiara[5]arenes (<b>T[5]</b>), a rim-differentiated pillar[5]arene derivative. By meticulously exploring the conformational space, we have successfully identified a multitude of distinct <b>T[5]</b> conformers within a relatively narrow energy range of 22 kJ/mol. This finding underscores the inherent conformational flexibility of this macrocyclic scaffold, enabling <b>T[5]</b> to adapt diverse packing arrangements in the solid state. While solvent-free <b>T[5]</b> crystals do not exhibit permanent porosity, they undergo solvomorphic interconversions when exposed to various guest compounds. Our study demonstrates that <b>T[5]</b>-based crystalline materials exhibit a notable preference for selectively capturing aromatic and olefinic solvents, such as benzene, toluene, chlorobenzene, and cyclohexene, over their aliphatic hydrocarbon counterparts from equivalent volume liquid mixtures, achieving up to 10:1 selectivity between benzene and cyclohexane.JACS AuGuest-Induced Conformational Transformations in Tiara[5]arene Crystals: A Pathway for Molecular Sieving.PMC114233312022M71213721JC14017002237124122001169SN-ZJU-SIAS-00622205143Liu HYang WJiang SXu ZSue ACfalseGuest-Induced Conformational Transformations in Tiara[5]arene Crystals: A Pathway for Molecular Sieving.In pursuit of environmental sustainability and energy efficiency, assorted macrocyclic compounds have recently emerged as crystalline adsorbents for the efficient molecular sieving of various chemical commodities. Herein, we delve into the conformational characteristics and solid-state packing modes of tiara[5]arenes (<b>T[5]</b>), a rim-differentiated pillar[5]arene derivative. By meticulously exploring the conformational space, we have successfully identified a multitude of distinct <b>T[5]</b> conformers within a relatively narrow energy range of 22 kJ/mol. This finding underscores the inherent conformational flexibility of this macrocyclic scaffold, enabling <b>T[5]</b> to adapt diverse packing arrangements in the solid state. While solvent-free <b>T[5]</b> crystals do not exhibit permanent porosity, they undergo solvomorphic interconversions when exposed to various guest compounds. Our study demonstrates that <b>T[5]</b>-based crystalline materials exhibit a notable preference for selectively capturing aromatic and olefinic solvents, such as benzene, toluene, chlorobenzene, and cyclohexene, over their aliphatic hydrocarbon counterparts from equivalent volume liquid mixtures, achieving up to 10:1 selectivity between benzene and cyclohexane.2024-01-01T00:00:00Z2024 Sep2026-06-04T16:48:06.501Z2025-04-06T16:23:30.595ZS-EPMC114233313932875810.1021/jacsau.4c00310