ࡱ> "$!] &bjbj A0xx{jj""E#E#E#Y#Y#Y#8#L#$Y#C$()$)$)$)$===?CACACACACACAC$EHeC-E#===^==eC"")$)$dC@@@=")$"l)$?C@=?C@@#,@)$ͻ{Y#{?|@+CC0C@,I?,I@,IE#@X@===eCeC@===C====,I=========j s!:  Metal Cation Complexes with Tetrapyridine Macrocyclic Ligands  DFT Calculations Ines Despotovi Quantum Organic Chemistry Group, Division of Organic Chemistry and Biochemistry, Ruer Boakovi Institute, 10000 Zagreb, Croatia e-mail: Ines.Despotovic@irb.hr Abstract It is well known that macrocyclic compounds have ability to form stable complexes with metal ions of appropriate dimensions. The cation possessing the best fit for the cavity in question will have the largest complexation energy. Therefore, the macrocycles can be potentially used for the separation of the specific metal ions [1]. Very interesting macrocyclic structures are provided by systems containing polypiridine building fragments [2]. The binding ability of metal cations is enabled through the interaction with the lone electron pairs of the nitrogen atoms. In the present work we have considered complexation of Li+, Na+, Be2+ and Mg2+ metal cations with systems 1 and 2 containing four pyridine subunits, both in the gas phase and in acetonitrile solution.  EMBED ChemDraw.Document.6.0  EMBED ChemDraw.Document.6.0  R=H, NMe2 1 2 Gas phase molecular structures and complexation energies were calculated by the B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) method including basis set superposition error (BSSE) calculated by counterpoise (CP) correction scheme at the same level of theory. The solvent effects were assessed using the polarized continuum method (PCM). It is found that Be2+ cation has the largest interaction energies in systems 1 and 2. The corresponding gas phase binding enthalpies are -484.6 kcal mol-1 (1, R=H), -540.0 kcal mol-1 (1, R=NMe2), -521.6 kcal mol-1 (2, R=H) and -553.8 kcal mol-1 (2, R=NMe2). The log K values in acetonitrile are 37.9, 51.7, 46.7 and 58.3 units, respectively. Acknowledgments: The financial support of The Croatian Ministry of Science, Education and Sports through grant No. 098-0982933-2911 is gratefully acknowledged. References: [1] R. M. Izatt, K. Pawlak, J. S. Bradshaw R. L. Bruening, Chem. Rev. 91 (1991) 1721. [2]<|~ f h ʶ좍{iWE3EW#he56CJOJQJ\^JaJ#h,56CJOJQJ\^JaJ#h~}56CJOJQJ\^JaJ#h/R56CJOJQJ\^JaJ#h&56CJOJQJ\^JaJ)hAwh(k56CJOJQJ\^JaJ&h&56>*CJOJQJ\^JaJ&hAwh(k5CJOJQJ\^JaJ h&5CJOJQJ\^JaJ hADI$t$x$z$|$$$$$$$$$$$$$$$$$$$޶qc[h70J7CJjh7UmHnHu5jh76B*CJU]mHnHphsH 4tH 4uhO~jhO~U hAwhzmCJOJQJ^JaJhAwhzmOJQJ^J#hAwh(kCJOJQJ\^JaJU&hEehEe5CJOJQJ\^JaJhEeCJOJQJ\^JaJ#hEehEeCJOJQJ\^JaJ I. Despotovi, B. Kova evi, Z. B. Maksi, New. J. Chem. 31 (2007) 447.       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