Pinning Down Small Populations of Photoinduced Intermediates Using Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory Difference Spectra to Provide Mechanistic Insight into Controlling Pyridine Azo Dynamics with Protons.

In this work, the impact of protonation on the photoisomerization ( → ) and reversion ( → ) of three pyridine-based azo dyes () is investigated by using a combination of transient absorption spectroscopy and time-dependent density functional theory computed difference spectra. The photophysical behaviors of the dyes are altered by the addition of one or two protons. Protonation of basic pyridine nitrogens results in an ultrafast accelerated reversion mechanism after photoisomerization, while protonation of azo bond nitrogens restricts isomer formation entirely.

Controlling excited-state dynamics protonation of naphthalene-based azo dyes.

Azo dyes are a class of photoactive dyes that constitute a major focus of chemical research due to their applications in numerous industrial functions. This work explores the impact of protonation on the photophysics of four naphthalene-based azo dyes. The p value of the dyes increases proportionally with decreasing Hammett parameter of -phenyl substituents from 8.

Ultra-fast excited-state dynamics of substituted -naphthalene azo moieties.

In this work we untangle the ultrafast deactivation of high-energy excited states in four naphthalene-based azo dyes. Through systematic photophysical and computational study, we observed a structure-property relationship in which increasing the electron donating strength of the substituent leads to longer lived excited states in these organic dyes and faster thermal reversion from the to configuration. In particular, azo dyes 1-3 containing less electron donating substituents show three distinct excited-state lifetimes of ∼0.

Elucidation of complex triplet excited state dynamics in Pd(II) biladiene tetrapyrroles.

Pd(II) biladienes have been developed over the last five years as oligotetrapyrrole complexes that support a rich triplet photochemistry. In this work, we have undertaken the first detailed photophysical interrogation of three homologous Pd(II) biladienes bearing different combinations of methyl- and phenyl-substituents on the frameworks' sp-hybridized -carbon (, the 10-position of the biladiene framework). These experiments have revealed unexpected excited-state dynamics that are dependent on the wavelength of light used to excite the biladiene.