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Updated: Jul 8, 2025

Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
Published on: June 10, 2021
Photophysical Outcomes of Water-Solvated Heterocycles: Single-Conformation Ultraviolet and Infrared Spectroscopy of
Ruby W Neisser1, John P Davis1, Megan E Alfieri1
1Department of Chemistry, The College of William & Mary, Williamsburg, Virginia 23187-8795, United States.
Abstract:
The molecular chromophores within brown carbon (BrC) aerosols absorb solar radiation at visible and near-ultraviolet wavelengths. This contributes to the overall warming of the troposphere and the photochemical aging of aerosols. In this investigation, we combine a suite of experimental and theoretical methods to reveal the conformation-specific ultraviolet and infrared spectroscopy of 2-phenylpyrrole (2PhPy)─an extended π-conjugated pyrrole derivative and a model BrC chromophore─along with its water microsolvated molecular complexes (2PhPy:nH2O, n = 1-3). Using resonant two-photon ionization and double-resonance holeburning techniques alongside MP3 (ground state) and ADC(3) (excited state) torsional potential energy surfaces and discrete variable representation simulations, we characterized the ultraviolet spectra of 2PhPy and 2PhPy:1H2O. This analysis revealed evidence for Herzberg-Teller vibronic coupling along the CH wagging and NH stretching coordinates of the aromatic rings. Conformation-specific infrared spectroscopy revealed extended hydrogen-bonding networks of the 2PhPy:nH2O complexes. Upon stepwise addition of H2O solvation, the nearest H2O acceptor forms a strong, noncovalent interaction with the pyrrole NH donor, while the second and third H2O partners interface with the phenyl and pyrrole aromatic rings through growing van der Waals π/H atom stabilization. A local-mode Hamiltonian approach was employed for comparison with the experimental spectra, thus identifying the vibrational spectral signatures to specific 2PhPy:nH2O oscillators.
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