Bond Alternation, Polarizability and Resonance Detuning in Methine Dyes

TL;DR

This paper develops structure-property relationships for methine dyes, linking their color and polarizability to bond alternation and charge resonance, with applications to biomolecular chromophores like GFP.

Contribution

It introduces a novel approach to parameterize the Platt model using spectroscopic data, enabling analysis of dyes without synthesizing symmetric parent compounds.

Findings

Platt model provides an alternative route to structure-property relationships.

Spectroscopic data can be used to parameterize the model without synthesis.

Application to GFP chromophores demonstrates practical utility.

Abstract

We derive structure-property relationships for methine ("Brooker") dyes relating the color of the dye and its symmetric parents to its bond alternation in the ground state and also to the dipole properties associated with its low-lying charge-resonance (or charge-transfer) transition. We calibrate and test these relationships on an array of different protonation states of the green fluorescent protein chromophore motif (an asymmetric halochromic methine dye) and its symmetric parent dyes. The relationships rely on the assumption that the diabatic states that define the Platt model for methine dye color [J.R. Platt, J. Chem. Phys. 25 80 (1956)] can also be distinguished by their single-double bond alternation and by their charge localization character. These assumptions are independent of the primary constraint that defines the diabatic states in the Platt model - specifically, the Brooker deviation rule for methine dyes [L.G.S. Brooker, Rev. Mod. Phys. 14 275 (1942)]. Taking these assumptions, we show that the Platt model offers an alternate route to known structure-property relationships between the bond length alternation and the quadratic nonlinear polarizability {\beta}. We show also that the Platt model can be parameterized without the need for synthesis of the symmetric parents of a given dye, using dipole data obtained through spectroscopic measurements. This suggests that the Platt model parameters may be used as independent variables in free-energy relationships for chromophores whose symmetric parents cannot be synthesized or chromophores strongly bound to biomolecular environments. The latter category includes several recently characterized biomolecular probe constructs. We illustrate these concepts by an analysis of previously reported electroabsorption and second-harmonic generation experiments on green fluorescent proteins.