Elroby, Shabaan A. K. Lee, Kyu Hwan Oh, Jung Soo Chung, Hwan Won Cho, Seung Joo Paek, Kyungsoo 2024-01-21T01:06:20Z 2024-01-21T01:06:20Z 2021-08-31 2007-03-15 0020-7608 https://pubs.kist.re.kr/handle/201004/134535 Fluorospherands (F-spherands) are highly preorganized hosts composed of fluorobenzene or 4-methylfluorobenzene units attached to one another at their 2,6-positions. To understand the intrinsic factors affecting cation complexation, we investigated the complexation behavior between F-spherands and cations using density functional theory (DFT) at the level of B3LYP/6-31G**. The F6-spherand (C6H3F)(6), (1) has a highly preorganized spherical cavity, which can encapsulate Li+ and Na+. Its cavity is not big enough for K+ and NH4+, which prefer external binding. Plausible conformations were studied for F8-spherand (C6H3F)(8). Conformer of D-2d symmetry (2b) is more stable than that of D-4d (2a), in agreement with NMR experiments. The cavity size of F8-spherand is big enough to encapsulate all cations studied. However, the cavity size of 2b is smaller than that of 2a, which resulted in the guest selectivity. Upon complexation, 2b conformation is more stable for Li+ and Na+, while 2a conformation is preferred for larger cations such as K+ and NH4+. Thus, the ab initio calculations over 4 these highly preorganized fluorospherands give important insights into their host-guest chemistry. (c) 2006 Wiley Periodicals, Inc. English JOHN WILEY & SONS INC GUEST COMPLEXATION ALKALI SELECTIVITY SPHERANDS TRANSPORT LIGANDS IONS POLYETHERS MEMBRANES CHEMISTRY Reorganization of highly preorganized hosts upon cation complexation: Ab initio study of fluorospherands Article 10.1002/qua.21208 1 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, v.107, no.4, pp.930 - 936 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 107 4 930 936 scie scopus 000243580100015 2-s2.0-33846699371 Chemistry, Physical Mathematics, Interdisciplinary Applications Quantum Science & Technology Physics, Atomic, Molecular & Chemical Chemistry Mathematics Physics Article GUEST COMPLEXATION ALKALI SELECTIVITY SPHERANDS TRANSPORT LIGANDS IONS POLYETHERS MEMBRANES CHEMISTRY fluorospherand complexation selectivity density functional theory