title: Synthesis, structure, electronic and vibrational spectra of 9-(Diethylamino)-benzo(a)phenoxazin-7-ium-5-N-methacrylamide.
abstract: The electronic and vibrational spectra of 9-(Diethylamino)-benzo(a)phenoxazin-7-ium-5-N-methacrylamide (Nile Blue-5-N-methacrylamide) are measured, and the results are compared with the theoretical values obtained by quantum chemical calculations. The geometry, electronic transitions, charge distribution, and the IR normal modes of this new dye and of its precursor Nile Blue have been computed by using Density Functional Theory (DFT) method with the functional B3LYP and the 6-31G(d) Gaussian basis set. The molecular properties of the two dyes, predicted and observed, are very similar in the electronic ground state. In the excited state, however, the longer lifetime and larger fluorescence quantum yield of the Nile Blue-5-methacrylamide is ascribed to an inhibition of the twisted intramolecular charge transfer (TICT) process, when the NH2 is substituted by the methacrylamide in the 5-position of the aromatic extended ring of the dye. The change in charge density of the N atom in 5-position, as well as the difference in dipole moment and ionization potential of the two dyes molecules, explain the attenuation of TICT process. The vibration spectra of both dyes are simulated properly by using the DFT method.
authors.affiliation: Instituto de Química de São Carlos, Universidade de São Paulo, CP 780, CEP 13560-970 Sao Carlos, SP, Brazil.
authors.forename: H P M
authors.initials: HP
authors.lastname: Oliveira
authors.forename: A J
authors.initials: AJ
authors.lastname: Camargo
authors.forename: L G
authors.initials: LG
authors.lastname: Macedo
authors.forename: M H
authors.initials: MH
authors.lastname: Gehlen
authors.forename: A B F
authors.initials: AB
authors.lastname: da Silva
mesh_terms: D007834:Lasers; D008689:Methacrylates / Q000138:chemical synthesis / Q000737:chemistry*; D010078:Oxazines / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: C474942:9-(diethylamino)-benzo(a)phenoxazin-7-ium-5-N-methacrylamide; D008689:Methacrylates; D010078:Oxazines; C008384:methacrylic acid; C008619:Nile Blue