Rotational isomers (rotamers) of substituted aromatic molecules exhibit distinct physicochemical properties that are fundamental to understanding their reactivity and biological functions. However, resolving individual rotamers spectroscopically remains challenging due to their similar transition energies and overlapping spectral features. Herein, we report the conformer-specific identification and characterization of three stable rotamers of m-ethoxyphenol using a combination of resonance-enhanced multiphoton ionization (REMPI), hole-burning (HB) spectroscopy, and mass-analyzed threshold ionization (MATI) techniques, complemented by high-level quantum chemical calculations at the B3PW91/aug-cc-pVTZ and G4 levels of theory. The S₁ ← S₀ electronic origins of rotamers I, IV, and III were determined to be 35,966 ± 2, 36,031 ± 2, and 36,198 ± 2 cm⁻¹, respectively, while their corresponding adiabatic ionization energies (IEs) were precisely measured as 64,574 ± 5, 64,122 ± 5, and 64,994 ± 5 cm⁻¹. The vibrational spectra of both the S₁ excited state and the D₀ cationic ground state were assigned, with most active modes corresponding to in-plane benzene ring vibrations. Structural analysis reveals that the benzene ring undergoes slight expansion upon S₁ ← S₀ excitation and contraction upon D₀ ← S₁ ionization, while the overall molecular geometry remains remarkably similar across all three electronic states, a key factor underlying the excellent agreement between experimental and simulated Franck–Condon spectra. Comparison with m-methoxyphenol demonstrates that the stronger electron-donating ability of the ethoxy group leads to systematically lower excitation and ionization energies. The distinct spectroscopic fingerprints established herein provide a definitive reference for identifying specific m-ethoxyphenol rotamers in future studies of this molecule and its complexes.

m-Aminostyrene (MAS) is a key molecular scaffold with an electron-donating amino group and a conjugating vinyl group, exhibiting significant potential in photonic materials and biological applications due to its rotamerism and photoinduced behavior. Despite its importance, a comprehensive, rotamer-resolved investigation of its vibronic and cationic spectroscopic properties is lacking. Here, we report a high-resolution study on the cis and trans rotamers of jet-cooled MAS using two-color resonant enhanced multi-photon ionization (2C-REMPI), UV-UV hole-burning (HB), and mass-analyzed threshold ionization (MATI) spectroscopies, combined with density functional theory (DFT) calculations. The HB technique unambiguously resolves the vibronic spectra of each rotamer, overcoming the limitations of previous one-color REMPI studies. The excitation energies (S₁ ← S₀) are determined to be 30,416 cm⁻¹ (cis) and 30,932 cm⁻¹ (trans). The MATI spectra yield precise adiabatic ionization energies (AIEs) of 61,569 cm⁻¹ (cis) and 61,274 cm⁻¹ (trans). A comprehensive assignment of vibrational modes in both the S₁ and D₀ states is provided, revealing distinct mode activities and frequency shifts between the two rotamers. A propensity for Δν = 0 upon ionization is observed, indicating high geometrical similarity between the S₁ and D₀ states. This work provides a crucial spectroscopic blueprint for understanding the electronic and vibrational structure of MAS rotamers, with implications for the design of functionalized styrene-based molecular systems.

We report a comprehensive spectroscopic investigation of p-diethynylbenzene (pDEB) using two-color resonance-enhanced multiphoton ionization (REMPI) and mass-analyzed threshold ionization (MATI) spectroscopy, complemented by density functional theory (DFT) calculations. The S₁ ← S₀ electronic origin is observed at 34,255 ± 2 cm⁻¹. The adiabatic ionization energy (IE) is determined to be 69,095 ± 5 cm⁻¹ from two-color MATI spectra recorded via the S₁ origin. Notably, a narrow peak is observed at 32 cm⁻¹ above the IE in the two-color MATI spectrum, which is assigned to a one-color, two-photon accidental resonance arising from the near-resonant condition where the S₁ ← S₀ transition energy (34,255 cm⁻¹) is close to half of the IE (69,099/2 = 34,549.5 cm⁻¹). This observation is consistent with similar reports for p-chlorofluorobenzene and p-difluorobenzene. Franck–Condon simulations show good agreement with the experimental spectra. The present results provide a spectroscopic basis for identifying pDEB and distinguishing it from its ortho and meta isomers.