Spectroscopic characterization of the complexes of 2-(2'-pyridyl)-benzimidazole and (HO), (CHOH), and (NH) isolated in the gas phase.

The hydrogen-bonded docking preferences of small solvent molecules on 2-(2'-pyridyl)-benzimidazole (PBI) were studied experimentally aided by computational findings. The PBI-S complexes (S = HO, CHOH, and NH) were produced in a supersonically jet-cooled molecular beam and probed using resonant two-photon ionization and laser-induced fluorescence spectroscopy, with multiple isomers confirmed by UV-UV hole-burning spectroscopy. Two distinct isomers of PBI-HO and PBI-(HO) complexes were identified, while PBI-CHOH and PBI-NH each formed a single 1 : 1 and 1 : 2 complex. Computational results with experimental findings revealed PBI-S-a as the most stable structure, with a solvent molecule forming a hydrogen-bonded bridge between imidazolyl-NH (NH) and pyridyl-N (N) at site-a. The site-a isomers exhibit higher S state stability compared to the S state, resulting in red-shifted S → S band origin for PBI-S-a and a further red-shift for the PBI-(S)-aa isomers. In contrast, the PBI-S-b isomer, with a hydrogen bond between imidazolyl-N (N) and pyridyl-CH (CH) at site-b opposite to site-a, showed a blue-shifted band origin transition. A unique PBI-(HO)-ab isomer was detected with solvent molecules bound at both sites a and b, displaying a smaller red-shift in the band origin transition than the aa-isomer. The energy barrier for solvent-to-chromophore proton transfer varies with isomeric configuration. PBI-HO-b isomers show significantly higher barriers (>800 cm), while PBI-(HO)-aa has a slightly increased barrier (>436 cm) compared to the PBI-HO-a (420 ± 10 cm) isomer. This study explores the potential landscape of PBI, enhancing our understanding of stabilization effects, spectral shifts, and their impact on chromophore excited-state dynamics in various environments.