Synthesis, Optical Properties, and LFER Analysis of Solvent-Dependent Binding Constants of Hamilton-Receptor-Connected Merocyanine Chromophores

Abstract

A merocyanine dye equipped with a Hamilton-receptor unit has been synthesized that enables strong noncovalent binding of other merocyanine dyes bearing barbituric acid acceptor groups by six hydrogen bonds. NMR and UV/vis titration experiments in toluene, chloroform, dichloromethane, dioxane, and THF provide evidence for the formation of 1:1 complexes even in the dipolar solvents. An enhanced binding strength is observed for the more dipolar merocyanine dyes in the head-to-tail assembly structure with binding constants up to >10 (8) M (-1) in toluene. In the present bimolecular complexes two merocyanine chromophores are assembled in a head-to-tail fashion that affords increased dipole moments as demanded for efficient electric field induced poling processes in nonlinear optical and photorefractive polymeric hosts. The solvent dependency of the binding constants for various barbituric acid dye-Hamilton receptor complexes as well as a perylene imide-melamine complex reveals linear free energy relationships (LFER) that allow for an estimation of binding constants larger than 10 (12) M (-1) for Hamilton receptor organized head-to-tail merocyanine bimolecular complexes in aliphatic solvents. It is suggested that such LFER are valuable tools for the estimation of binding constants in solvents where experimental binding constants cannot be determined because of solubility or spectroscopic problems.