title: DFT study of the cryptand and benzocryptand and their complexes with alkali metal cations: Li+, Na+, K+.
abstract: In the present work, a theoretical study of the cryptand 4, 7, 13, 16, 21, 24-hexaoxa-1, 10- diazabicyclo [8,8,8] hexacosan (the named [222]) and the cryptand 5, 6-benzo-4, 7, 13, 16, 21, 24-hexaoxa-1, 10-diazabicyclo [8, 8, 8] hexacosan (the nemed [222B]) had been done using density functional theory (DFT) with B3LYP/6-31G* method in order to obtain the electronic and geometrical structure of the cryptands and their complexes with alkali metal ions: Li(+), Na(+), and K(+). The nucleophilicity of cryptands had been investigated by the Fukui function. For complexes, the match between cation and cavity size, the status of interaction between alkali metal ions and donor atoms in the cryptands and the rigidity of the cryptands had been analyzed through the other calculated parameters. In addition, the enthalpies of complexation reaction and cation exchange reaction had been studied by the calculated thermodynamic data. The calculated results are in a good agreement with the experimental data for the complexes.
authors.affiliation: Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, People's Republic of China. wxueye@xtu.edu.cn
authors.forename: Xueye
authors.initials: X
authors.lastname: Wang
authors.forename: Hengliang
authors.initials: H
authors.lastname: Wang
authors.forename: Yuanqiang
authors.initials: Y
authors.lastname: Tan
mesh_terms: D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D002412:Cations / Q000737:chemistry; D003198:Computer Simulation; D043844:Crown Ethers / Q000737:chemistry*; D004583:Electrons; D008672:Metals, Alkali / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D002412:Cations; D043844:Crown Ethers; D008672:Metals, Alkali; D009942:Organometallic Compounds