Effect of stereoconfiguration of aromatic ligands on retention and selectivity of terphenyl isomer-bonded stationary phases

Abstract

The structure of ligands has a significant influence on the separation properties of alkyl and aromatic phases in reversed-phase liquid chromatography. Compared with alkyl phases, the effect of stereoconfiguration of aromatic ligands on the retention and selectivity of stationary phases has rarely been addressed. To illustrate the issue, three terphenyl isomer-bonded stationary phases were prepared via the coupling chemistry of isocyanate with terphenyl amine isomers, 3,4-diphenylaniline, 2,4-diphenylaniline and 4-amino-p-terphenyl, respectively. The retention behaviors of stationary phases were assessed in terms of retention strength, selectivity, hydrophobic and π-π interaction by five kinds of solutes. It is found that the selectivity towards the solutes is slightly larger on the branched m-terphenyl-bonded phase (m-π3) than o-terphenyl-bonded phase (o-π3) but is significantly improved on the chain p-terphenyl-bonded phase (p-π3). The results can be interpreted by the ease self-adjustment of the conformation of the chain p-terphenyl ligand and the smaller steric effect of p-π3 towards the insertion of solutes into the ligand brushes. In addition, the p-π3 yields excellent selective separation towards aromatic solutes. These findings are of significance in the design of aromatic stationary phases.