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Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy.

ABSTRACT: Azobenzene, a versatile and polymorphic molecule, has been extensively and successfully used for photoswitching applications. The debate over its photoisomerization mechanism leveraged on the computational scrutiny with ever-increasing levels of theory. However, the most resolved absorption spectrum for the transition to S1(n?*) has not followed the computational advances and is more than half a century old. Here, using jet-cooled molecular beam and multiphoton ionization techniques we report the first high-resolution spectra of S1(n?*) and S2(??*). The photophysical characterization reveals directly the structural changes upon excitation and the timescales of dynamical processes. For S1(n?*), we find that changes in the hybridization of the nitrogen atoms are the driving force that triggers isomerization. In combination with quantum chemical calculations we conclude that photoisomerization occurs along an inversion-assisted torsional pathway with a barrier of ~2 kcal mol(-1). This methodology can be extended to photoresponsive molecular systems so far deemed non-accessible to high-resolution spectroscopy.

SUBMITTER: Tan EM

PROVIDER: S-EPMC4308720 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature

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Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy.

Tan Eric M M EM Amirjalayer Saeed S Smolarek Szymon S Vdovin Alexander A Zerbetto Francesco F Buma Wybren Jan WJ

Nature communications 20150106

Azobenzene, a versatile and polymorphic molecule, has been extensively and successfully used for photoswitching applications. The debate over its photoisomerization mechanism leveraged on the computational scrutiny with ever-increasing levels of theory. However, the most resolved absorption spectrum for the transition to S1(nπ*) has not followed the computational advances and is more than half a century old. Here, using jet-cooled molecular beam and multiphoton ionization techniques we report th ...[more]

PMID: 25562840

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Project description:The non-heme ferryl active sites are of significant interest for their application in biomedical and green catalysis. These sites have been shown to have an S = 1 or S = 2 ground spin state; the latter is functional in biology. Low-temperature magnetic circular dichroism (LT MCD) spectroscopy probes the nature of the excited states in these species including ligand-field (LF) states that are otherwise difficult to study by other spectroscopies. In particular, the temperature dependences of MCD features enable their unambiguous assignment and thus determination of the low-lying excited states in two prototypical S = 1 and S = 2 NHFe(IV)[double bond, length as m-dash]O complexes. Furthermore, some MCD bands exhibit vibronic structures that allow mapping of excited-state interactions and their effects on the potential energy surfaces (PESs). For the S = 2 species, there is also an unusual spectral feature in both near-infrared absorption and MCD spectra - Fano antiresonance (dip in Abs) and Fano resonance (sharp peak in MCD) that indicates the weak spin-orbit coupling of an S = 1 state with the S = 2 LF state. These experimental data are correlated with quantum-chemical calculations that are further extended to analyze the low-lying electronic states and the evolution of their multiconfigurational characters along the Fe-O PESs. These investigations show that the lowest-energy states develop oxyl Fe(III) character at distances that are relevant to the transition state (TS) for H-atom abstraction and define the frontier molecular orbitals that participate in the reactivity of S = 1 vs. S = 2 non-heme Fe(IV)[double bond, length as m-dash]O active sites. The S = 1 species has only one available channel that requires the C-H bond of a substrate to approach perpendicular to the Fe-oxo bond (the ? channel). In contrast, there are three channels (one ? and two ?) available for the S = 2 non-heme Fe(IV)[double bond, length as m-dash]O system allowing C-H substrate approach both along and perpendicular to the Fe-oxo bond that have important implications for enzymatic selectivity.

Dataset Information

Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy.

Publications

Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy.

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