Probing Surface Basicity of Solid Acids with an Aminobenzodifurandione Dye as the Solvatochromic Probe

Abstract

Solvatochromism and sorptiochromism of the dye 3-(4-amino-3-methylphenyl)-7-phenyl-benzo1,2b:4,5b'difuran-2,6-dione (1) are studied with an extended set of solvents and various solid acids including silicas, aluminas, and alumosilicates. 1 shows a positive solvatochromism with increasing basicity and dipolarity/polarizability of the solvent; its solvent-induced bathochromic UV-vis absorption band shift ranges from formic acid (upsilon(max) = 21 630 cm(-1)) to hexamethylphosphoric acid triamide (upsilon(max) = 14 200 cm(-1)). Multiple square analyses of upsilon(max) of the solvent-dependent solvatochromic UV-vis absorption band of 1 with several empirical solvent polarity parameters prove that a composite of basicity, acidity, and dipolarity/polarizability of the environment must be taken into account. For the analysis of the solvent-dependent UV-vis shift of 1, the Kamlet-Taft and Catalan solvent parameters have been evaluated. It could be shown that the Catalan solvent parameter set is more suitable to reflect multiple solvation processes involving both strong basic and strong acidic solvents. Quantum chemical calculations indicate that an interaction of the silanol oxygen atom with the protons of the amino group is clearly favored over various acidic attacks of silanol groups upon 1. Accordingly, surface basicity of silica, alumina, and alumosilicates can be determined using the linear solvation energy relationship derived from the solvent-dependent UV-vis band of 1. An unambiguous interpretation of the UV-vis spectroscopic data of 1 adsorbed on surfaces containing Lewis-acid sites is sometimes difficult. UV-vis monitoring of 1-loaded solid acids during surface titration with 2,6-di-tert-butyl pyridine allows the discrimination of whether Brønsted- or Lewis-acid sites interfere with 1. Additionally, adsorbed water has an important influence on the actual surface basicity of solid acids. 1 is recommended as a sensitive probe for checking both basicity and acidity when directly compared with solvatochromism of the established hydrogen-bond-donating indicator (cis-dicyano)bis(1,10-phenanthroline)iron(II) (2).