title: Spectral tuning by switching C-H[...]O hydrogen bonds: rotation-induced spectral shifts of 7-hydroxyquinoline HCOOH isomers.
abstract: Spectral tuning effects on visible chromophores by hydrogen bonds are central to the chemistry of vision and of photosynthesis. A model for large spectral tuning effects by hydrogen bond switching is provided by the 7-hydroxyquinoline x HCOOH complex, which forms two isomers, CTN1 and CTN2, both with an HCOOH[...]N hydrogen bond but with different (quinoline)C-H[...]O=C hydrogen bonds. A 180 degrees rotation of the HCOOH moiety around the O-H[...]N hydrogen bond exchanges the C-H[...]O hydrogen bonds, rotates the dipole moment of HCOOH, and leads to an approximately 850 cm(-1) shift of the electronic spectrum. Mass-selected S1<--S0 resonant two-photon ionization, UV-UV holeburning, S1-->S0 fluorescence spectra, and photoionization efficiency curves of the two 7-hydroxyquinoline x HCOOH isomers were measured in supersonic expansions. Comparison to ab initio calculations allow us to determine the H-bond connectivity and structure of the two isomers and to assign their inter- and intramolecular vibrations. The Franck-Condon factors of the intermolecular shear vibration chi in the S1<--S0 spectra indicate that the weak C-H[...]O hydrogen bond contracts markedly in the CTN1 isomer but expands in the CTN2 isomer. These changes of H-bond lengths agree with the spectral shifts. In contrast, the strong O-H[...]N hydrogen bond undergoes little change upon S1[...]S0 excitation.
authors.affiliation: Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3000 Bern 9, Switzerland.
authors.forename: Markus
authors.initials: M
authors.lastname: Thut
authors.forename: Carine
authors.initials: C
authors.lastname: Manca
authors.forename: Christian
authors.initials: C
authors.lastname: Tanner
authors.forename: Samuel
authors.initials: S
authors.lastname: Leutwyler