Abstract
The effect of the local interaction of a metal ion with the solvent on the conformations of calcium complexes of arylazacrown ethers and an azacrown-containing dye was studied using the density functional method with the PBE and B3LYP functionals. The structures were studied and the interaction energies were determined for the calcium complexes with n = 1–12 water or acetonitrile molecules. It was found that the inner coordination sphere of the free Ca2+ cation contains six H2O or seven MeCN molecules. The cation—acetonitrile interaction energy is higher than the cation—water interaction energy up to the moment the second solvation shell of the cation is almost complete (n = 11). The inner coordination sphere of Ca2+ in the macrocycle cavity contains at most three water molecules, while the fourth one is displaced to the second coordination sphere. Taking into account the local interaction with the solvent (H2O or MeCN), the conformers of the calcium complexes of arylazacrown ethers and the azacrown-containing dye were studied. It was shown that the presence of two to four water molecules in the coordination sphere of the cation reduces the relative energies of the conformers with broken metal—nitrogen bond, thus favoring ground-state metal recoordination.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. Ya. Freidzon, A. A. Bagatur’yants, S. P. Gromov, and M. V. Alfimov, Izv. Akad. Nauk, Ser. Khim., 2003, 2505 [Russ. Chem. Bull., Int. Ed., 2003, 52, 2646].
E. N. Ushakov, S. P. Gromov, O. A. Fedorova, and M. V. Alfimov, Izv. Akad. Nauk, Ser. Khim., 1997, 484 [Russ. Chem. Bull., 1997, 46, 463 (Engl. Transl.)].
S. P. Gromov and M. V. Alfimov, Izv. Akad. Nauk, Ser. Khim., 1997, 641 [Russ. Chem. Bull., 1997, 47, 611 (Engl. Transl.)].
S. I. Druzhinin, M. V. Rusalov, B. M. Uzhinov, S. P. Gromov, S. A. Sergeev, and M. V. Alfimov, J. Fluoresc., 1999, 9, No. 1, 33.
S. I. Druzhinin, S. P. Gromov, M. V. Alfimov, and K. A. Zachariasse, XX Int. Conf. on Photochemistry (Moscow, July 30–August 4, 2001), Moscow, 2001, 299.
M. B. More, D. Ray, and P. B. Armentrout, J. Am. Chem. Soc., 1999, 121, 417.
D. Feller, J. Phys. Chem. A, 1997, 101, 2723.
D. Feller, M. A. Thompson, and R. A. Kendall, J. Phys. Chem. A, 1997, 101, 7292.
E. D. Glendening and D. Feller, J. Phys. Chem., 1996, 100, 4790.
I. K. Lednev, R. E. Hester, and J. N. Moore, J. Chem. Soc., Faraday Trans. 2, 1997, 93, 1551.
Cambrige Structural Database System, Version 5.23, 2002.
K. Rurack, J. L. Bricks, G. Reck, R. Radeglia, and U. Resch-Genger, J. Phys. Chem. A, 2000, 104, 3087.
J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865.
D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople, GAUSSIAN 98, Revision A.9, Gaussian, Inc., Pittsburgh (PA), 1998.
K. Kubo, E. Yamamoto, N. Kato, and A. Mori, Acta Crystallogr., Sect. C (Cr. Str. Commun.), 1999, 55, 1819.
E. M. Cabaleiro-Lago and M. A. Rios, Chem. Phys., 2000, 254, 11.
M. S. Islam, R. A. Pethrick, and D. Pugh, J. Phys. Chem. A, 1998, 102, 2201.
D. Feller, E. D. Glendening, D. E. Woon, and M. W. Feyereisen, J. Chem. Phys., 1995, 103, 3526.
E. D. Glendening and D. Feller, J. Phys. Chem., 1995, 99, 3060.
I. Dzidic and P. Kebarle, J. Phys. Chem., 1970, 74, 1466.
W. R. Davidson and P. Kebarle, J. Am. Chem. Soc., 1976, 98, 6125.
A. A. Bagatur’yants, A. Ya. Freidzon, M. V. Alfimov, E. J. Baerends, J. A. K. Howard, and L. G. Kuz’mina, J. Mol. Struct. (THEOCHEM), 2002, 588, 55.
V. G. Avakyan S. P. Gromov A. I. Vedernikov S. N. Dmitrieva and M. V. Alfimov Izv. Akad. Nauk, Ser. Khim. 2004 25 [Russ. Chem. Bull., Int. Ed. 2004 53 24].
M. V. Alfimov, A. V. Churakov, Yu. V. Fedorov, O. A. Fedorova, S. P. Gromov, R. E. Hester, J. A. K. Howard, L. G. Kuz’mina, I. K. Lednev, and J. N. Moore, J. Chem. Soc., Perkin Trans. 2, 1997, 2249.
Author information
Authors and Affiliations
Additional information
Dedicated to Academician A.L. Buchachenko on the occasion of his 70th birthday.
For Part 1, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1981–1992, September, 2005.
Rights and permissions
About this article
Cite this article
Freidzon, A.Y., Bagatur’yants, A.A., Gromov, S.P. et al. Recoordination of a metal ion in the cavity of a crown compound: a theoretical study 2.* Effect of the metal ion— solvent interaction on the conformations of calcium complexes of arylazacrown ethers. Russ Chem Bull 54, 2042–2054 (2005). https://doi.org/10.1007/s11172-006-0076-7
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/s11172-006-0076-7