TY - JOUR
T1 - Theoretical study of subporphyrins
AU - Pichierri, Fabio
N1 - Funding Information:
I thank the financial support from the 21st century COE program ‘Giant Molecules and Complex Systems’ of MEXT hosted at Tohoku University.
PY - 2006/8/4
Y1 - 2006/8/4
N2 - We have characterized the ground-state geometries, electronic structures and IR spectra of a series of contracted porphyrinoids termed subporphyrins with the aid of density functional theory calculations. The calculations indicate that all molecules are not flat with curvatures that depend upon the type of substituent atoms present. The metal-free (M{double bond, long}2H) subporphyrin molecule (1) is characterized by a low-energy intramolecular hydrogen bond (N-H⋯N) and its HOMO-LUMO energy gap is ∼0.55 eV larger in magnitude than that of the metal-free porphyrin homologue. A minimal model of the frontier orbitals of 1 comprises two pair of nearly-degenerate HOMOs and LUMOs.
AB - We have characterized the ground-state geometries, electronic structures and IR spectra of a series of contracted porphyrinoids termed subporphyrins with the aid of density functional theory calculations. The calculations indicate that all molecules are not flat with curvatures that depend upon the type of substituent atoms present. The metal-free (M{double bond, long}2H) subporphyrin molecule (1) is characterized by a low-energy intramolecular hydrogen bond (N-H⋯N) and its HOMO-LUMO energy gap is ∼0.55 eV larger in magnitude than that of the metal-free porphyrin homologue. A minimal model of the frontier orbitals of 1 comprises two pair of nearly-degenerate HOMOs and LUMOs.
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U2 - 10.1016/j.cplett.2006.06.010
DO - 10.1016/j.cplett.2006.06.010
M3 - Article
AN - SCOPUS:33746042202
VL - 426
SP - 410
EP - 414
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 4-6
ER -