Separation performances of extended pillar[6]arenes, a new stationary phase for gas chromatography

Pillar[n]arenes (P[n]As, n = 5-10), a new generation of macrocyclic hosts, display interesting properties such as 3D π-electron cavity, host-guest interactions, good stability, and easy functionalization, which make these polymers very promising for separation applications. In particular, extended P[n]As (EP[n]As) show large-sized cavities, structural flexibility, cavity adaptability, and synthetic accessibility. These characteristics have been exploited in this work, which reports for the first time the investigation of two EP[n]As (LP6A-C10 and BpP6A-C10) as stationary phases for gas chromatography (GC). LP6A-C10 and BpP6A-C10 columns exhibited moderate polarity (average polarity 117 and 118) and high column efficiencies (3000 plates/m and 3235 plates/m). These columns achieved complete challenging separation of halogenated benzene, benzaldehyde, phenol, and aniline isomers, which are difficult to resolve due to their high resemblance in structures and properties. Experimental results demonstrate the high selectivity and inertness of the prepared columns and their distinct advantages if compared with commercial HP-5 and HP-35 columns. EP[n]As columns displayed good separation repeatability with RSD values of 0.01%-0.02 % for run-to-run, 0.01%-0.22 % for day-to-day, and 1.36-3.56 % for column-to-column. This work demonstrates the promising future of EP[n]A stationary phases for chromatographic separations.