Journal of Physical Chemistry A, Vol.107, No.35, 6785-6791, 2003
van der Waals complex and solvatochromism studies of substituted benzenes and naphthalenes
Laser induced fluorescence (LIF) and resonantly enhanced multiphoton ionization (REMPI) studies of van der Waals complexes of aniline and 4-aminobenzonitrile (4-ABN) with some polar solvents are reported. The 1+1 clusters of aniline with methanol, acetone, and water do not fluoresce. The REMPI spectrum of 1+1 cluster of aniline with methanol shows only a broad band, which indicates a large change in geometry between ground and excited states. For complexes of aniline with acetone or water, the 1+1 signals in the mass spectra are from the dissociation of larger clusters. The molecule 4-aminobenzonitrile forms fluorescent 1+1 clusters with methanol and acetonitrile which have emission spectra similar to that of uncomplexed 4-aminobenzonitrile. In the complexes, the broad background that appears in the emission spectrum occurs at lower excess energy. Solvatochromism studies of 4-fluorobenzonitrile (4-FBN), aniline, 4-ABN, 1-cyanonaphthalene (1-CNN), 1-aminonaphthalene (1-AMN), and 1-amino-4-cyanonaphthalene (p-AMCNN) are also reported. The solvatochromism study shows that those molecules giving rise to broad emission in the,,as phase (aniline, 4 4-ABN, 1-AMN, and p-AMCNN) have a large solvatochromic shift, implying that in solution their emitting excited states have larger dipole moments than those of the ground states. The molecules with sharp gas-phase spectra, 4-FBN and 1-CNN, have little or no solvatochromic shift in solution.