Solvatochromic Azamethine Dyes for Probing the Polarity of Gold‐Cluster‐Functionalized Silica Particles

Azamethine dyes of the merocyanine type [4-(N,N-di-n-butylamino)-2-methylphenyl]{2,4-di-keto-3-[N′-(n-hexyl)]-5-cyano-6-methyl-3-pyridinio}-1-azamethine (1) and [4-(N,N-diethylamino)-2-(N′-tert-butylcarboxy)-amidophenyl]-{2,4-diketo-3-[N″-(n-hexyl)]-5-cyano-6-methyl-3-pyridinio}-1-azamethine (2) have been used as surface-polarity indicators for gold-cluster-functionalized silica particles. Their UV/Vis absorption maxima range from about λ=600 to 700 nm as a function of solvent polarity and are clearly separated from the surface plasmon UV/Vis absorption band of gold (λ≈520–540 nm). Solvatochromism of both dyes has been investigated in 26 solvents of different polarity. The positive solvatochromic band shifts of 1 and 2 can be well expressed in terms of the empirical Kamlet–Taft solvent polarity parameters α and π*. They are mainly sensitive to the dipolarity/polarizability (π* term; 70–75 %) and HBD (hydrogen-bond donating) acidity (α term) of the solvent. Both dyes adsorb readily on functionalized silica samples from solutions in 1,2-dichloroethane or cyclohexane. The surface polarities of gold-cluster-functionalized silica particles, with and without co-adsorbed L-cysteine and poly(ethylenimine), have been investigated by using these solvatochromic dyes. The specific interaction of dye 2 with cysteine has been examined independently by quantum-chemical calculations by using the AM1 and PM3 methods.