Valence Topological Charge-Transfer Indices for Reflecting Polarity Correction for Heteromolecules 英文参考文献.docVIP

Molecules 2005, 10, 334-345 molecules ISSN 1420-3049 Valence Topological Charge-Transfer Indices for Reflecting Polarity: Correction for Heteromolecules Francisco Torrens Institut Universitari de Ciència Molecular, Universitat de València, Dr. Moliner 50, E-46100 Burjassot (València), Spain. http://www.uv.es/~icmol. Tel. +34 963 543 182, Fax +34 963 543 156, E-mail Francisco.Torrens@uv.es Received: 29 March 2004 / Accepted: 10 May 2004 / Published: 28 February 2005 Abstract: Valence topological charge-transfer (CT) indices are applied to the calculation of dipole moments μ. The μ calculated by algebraic and vector semisums of the CT indices are defined. The model is generalized for molecules with heteroatoms and corrected for sp3-heteromolecules. The ability of the indices for the description of the molecular charge distribution is established by comparing them with μ of the valence- isoelectronic series of cyclopentadiene, benzene and styrene. Two CT indices, μvec (vector semisum of vertex-pair μ) and μvecV (valence μvec) are proposed. The μvecV behaviour is intermediate between μvec and μexperiment. The correction is produced in the correct direction. The best results are obtained for the greatest group. Inclusion of the heteroatom in the π-electron system is beneficial for the description of μ, owing to either the role of additional p and/or d orbitals provided by the heteroatom or the role of steric factors in the π-electron conjugation. The steric effect is almost constant along the series and the dominating effect is electronic. Inclusion of the heteroatom enhances μ, which can improve the solubility of the molecule. For heteroatoms in the same group, the ring size and the degree of ring flattering are inversely proportional to their electronegativity. Keywords: Charge distribution; Dipole moment; Heteroatom; Isolelectroic series; Valence topological charge-transfer index Int