On-surface isostructural transformation from a hydrogen-bonded network to a coordination network for tuning the pore size and guest recognition

Abstract

Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H3btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N-H⋯N hydrogen bonds. While the H3btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag3(btim)] coordination networks based on double N-Ag-N bonds at 423 K, by virtue of the unconventional metal-acid replacement reaction (Ag reduces H+). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host-guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.