Theoretical Study of Intramolecular Interactions in Peri-Substituted Naphthalenes: Chalcogen and Hydrogen Bonds.
A theoretical study of the peri interactions, both intramolecular hydrogen (HB) and chalcogen bonds (YB), in 1-hydroxy-8YH-naphthalene, 1,4-dihydroxy-5,8-di-YH-naphthalene, and 1,5-dihydroxy-4,8-di-YH-naphthalene, with Y = O, S, and Se was carried out. The systems with a OH:Y hydrogen bond are the most stable ones followed by those with a chalcogen O:Y interaction, those with a YH:O hydrogen bond (Y = S and Se) being the least stable ones. The electron density values at the hydrogen bond critical points indicate that they have partial covalent character. Natural Bond Orbital (NBO) analysis shows stabilization due to the charge transfer between lone pair orbitals towards empty Y-H that correlate with the interatomic distances. The electron density shift maps and non-covalent indexes in the different systems are consistent with the relative strength of the interactions. The structures found on the CSD were used to compare the experimental and calculated results.
Irish Centre of High-End Computing, Grand Canal Quay, Dublin 2, Ireland.
Goar
G
Sánchez-Sanz
Instituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid, Spain. ibon@iqm.csic.es.
Ibon
I
Alkorta
Instituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid, Spain. iqmbe17@iqm.csic.es.
José
J
Elguero
D018011:Chalcogens / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008958:Models, Molecular; D008962:Models, Theoretical; D009281:Naphthalenes / Q000737:chemistry*
D018011:Chalcogens; D009281:Naphthalenes
MP2; chalcogen bonds; hydrogen bonds; interaction energy; intramolecular interactions; non-covalent interactions