Issue 44, 2017

Chromophores of chromophores: a bottom-up Hückel picture of the excited states of photoactive proteins

Abstract

Many photoactive proteins contain chromophores based on para-substituted phenolate anions which are an essential component of their electronic structure. Here, we present a reductionist approach to gain fundamental insight into the evolution of electronic structure as the chromophore increases in complexity from phenolate to that in GFP. Using frequency- and angle-resolved photoelectron spectroscopy, in combination with electronic structure theory, the onset of excited states that are responsible for the characteristic spectroscopic features in biochromophores are determined. A comprehensive, yet intuitive picture of the effect of phenolate functionalisation is developed based on simple Hückel theory. Specifically, the first two bright excited states can be constructed from a linear combination of molecular orbitals localised on the phenolate and para-substituent groups. This essential interaction is first observed for p-vinyl-phenolate. This bottom-up approach offers a readily accessible framework for the design of photoactive chromophores.

Graphical abstract: Chromophores of chromophores: a bottom-up Hückel picture of the excited states of photoactive proteins

Supplementary files

Article information

Article type
Paper
Submitted
23 Aug 2017
Accepted
18 Sep 2017
First published
18 Sep 2017

Phys. Chem. Chem. Phys., 2017,19, 29772-29779

Chromophores of chromophores: a bottom-up Hückel picture of the excited states of photoactive proteins

C. S. Anstöter, C. R. Dean and J. R. R. Verlet, Phys. Chem. Chem. Phys., 2017, 19, 29772 DOI: 10.1039/C7CP05766K

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