Experimental and DFT Studies: Novel Structural Modifications Greatly Enhance the Solvent Sensitivity of Live Cell Imaging Dyes

Structural modifications of previously reported merocyanine dyes (J. Am. Chem. Soc. 2003, 125, 4132–4145) were found to greatly enhance the solvent dependence of their absorbance and fluorescence emission maxima. Density functional theory (DFT) calculations have been performed to understand the differences in optical properties between the new and previously synthesized dyes. Absorption and emission energies were calculated for several new dyes using DFT vertical self-consistent reaction field methods (VSCRF). Geometries of ground and excited states were optimized with a Conductor-like screening model (COSMO) and self-consistent-field (SCF) methods. The new dyes have enhanced zwitterionic character in the ground state, and much lower polarity in the excited state, as shown by the DFT-VSCRF calculations. Consistently, the position of the absorption bands are strongly blue-shifted in more polar solvent (methanol compared to benzene) as predicted by the DFT spectral calculations. Inclusion of explicit H-bonding solvent molecules within the quantum model further enhances the predicted shifts, and is consistent with the observed spectral broadening. Smaller, but significant spectral shifts in polar versus nonpolar solvent are predicted and observed for emission bands. The new dyes show large fluorescence quantum yields in polar hydrogen bonding solvents; qualitatively, the longest bonds along the conjugated chain at the excited S1 state minimum are shorter in the more polar solvent, inhibiting photoisomerization. The loss of photostability of the dyes is a consequence of the reaction with and electron transfer to singlet oxygen, starting oxidative dye cleavage. The calculated vertical ionization potentials of three dyes I-SO, AI-SO(4), and AI-BA(4) in benzene and methanol are consistent with their relative photobleaching rates; the charge distributions along the conjugated chains for the three dyes are similarly predictive of higher reaction rates for AI-SO(4) and AI-BA(4) than for I-SO. Time dependent DFT (TDDFT) calculations were also performed on AI-BA(4); these were less accurate than the VSCRF method in predicting the absorption energy shift from benzene (C6H6) to methanol (MeOH)

Electronic structure in broken space- and spin- symmetry : applications to Fe-s proteins and clusters

We review the theoretical and experimental bases for introducing a spin Hamiltonian having a sum of Heisenberg and resonance delocalization terms for iron-sulfur proteins and clusters. We show how broken symmetry calculations can be used to give spin Hamiltonian parameters by diagonalizing the appropriate broken symmetry and high spin state matrices. These methods are applied to 3Fe and Zn3Fe clusters to give Heisenberg J values and resonance delocalization 13 values. The Zn cluster spin ground state is analyzed in detail. For all clusters, J(reduced)<J(oxidized) and, for all cubane clusters, the magnitude of B is much greater for the broken symmetry than for the high spin states, B»B'