title: 1H/2H NMR studies of geometric H/D isotope effects on the coupled hydrogen bonds in porphycene derivatives.
abstract: The 1H and 2H NMR spectra of porphycene (1), 2,3,6,7,12,13,16,17-octaethylporphycene (2), 2,7,12,17-tetra-n-propylporphycene (3), and 2,7,12,17-tetra-(tert-butyl)-3,6-13,16-dibenzo[cde;mno]porphycene (4) partially deuterated in the mobile proton sites are reported. These compounds exhibit two intramolecular NHN hydrogen bonds of increasing strength representing models of the concerted HH transfer in the parent compound, porphycene. The 1H chemical shifts of the mobile protons are correlated with the difference of the energies of the amino- and imino-N1s orbitals reported by Ghosh A.; Moulder J.; Bröring M.; Vogel E. Angew. Chem., Int. Ed. 2001, 113, 445-448. The chemical shifts of 4 indicate a reduced contribution of the aromatic ring current as compared to the other compounds which is associated to the nonplanarity of this molecule. The primary H/D isotope effects on the chemical shifts give information about the primary, secondary, and vicinal geometric isotope effects of the two inner hydrogen bonds of porphycenes. The vicinal effects indicate a cooperative coupling of the two hydrogen bonds which may favor a concerted double proton-transfer mechanism.
authors.affiliation: Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany.
authors.forename: Mariusz
authors.initials: M
authors.lastname: Pietrzak
authors.forename: Mohamed F
authors.initials: MF
authors.lastname: Shibl
authors.forename: Martin
authors.initials: M
authors.lastname: Bröring
authors.forename: Oliver
authors.initials: O
authors.lastname: Kühn
authors.forename: Hans-Heinrich
authors.initials: HH
authors.lastname: Limbach
mesh_terms: D003903:Deuterium / Q000737:chemistry*; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards; D015394:Molecular Structure; D011166:Porphyrins / Q000737:chemistry*; D011522:Protons; D012015:Reference Standards; D012680:Sensitivity and Specificity
chemical_list: C519018:2,3,6,7,12,13,16,17-octaethylporphycene; C519020:2,7,12,17-tetra-(tert-butyl)-3,6-13,16-dibenzo(cde-mno)porphycene; C519019:2,7,12,17-tetra-n-propylporphycene; D011166:Porphyrins; D011522:Protons; C051407:porphycene; D003903:Deuterium