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1. Proton Pachinko: Probing Excited‐State Intramolecular Proton Transfer of St. John's Wort‐Derived Fluorescent Photosensitizer Hypericin with Ultrafast Spectroscopy**

   https://doi.org/10.1002/chem.202500639  

   Johnson, Seth_L; Krueger, Taylor_D; Solaris, Janak; Chen, Cheng; Fang, Chong (March 2025, Chemistry – A European Journal)

   Abstract Hypericin from St. John's wort has been used as a potent photosensitizer, but its working mechanism remains elusive which hinders its rational design for improved functionality. We implement ultrafast spectroscopy and quantum calculations to track the excited‐state dynamics in an intricate hydrogen‐bonding network of hypericin in solution. Using femtosecond transient absorption (fs‐TA), we track excited state intramolecular proton transfer (ESIPT) via a previously unreported blueshift of a long‐wavelength stimulated emission (SE) band with excitation‐dependent dynamics in various solvents, owing to the dominant Q^7,14tautomer that undergoes bidirectional ESIPT. This finding is corroborated by ground‐state femtosecond stimulated Raman spectroscopy (GS‐FSRS) and density functional theory (DFT) calculations. Moreover, contrasting the neutral and anionic forms of hypericin enables us to reveal an intramolecular charge transfer step underlying ESIPT. We demonstrate UV and visible excitations as an integral platform to provide direct insights into the photophysics and origin for phototoxicity of hypericin. Such mechanistic insights into the excited state of hypericin will power its future development and use. 

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2. Photogrammetry of Ultrafast Excited-State Intramolecular Proton Transfer Pathways in the Fungal Pigment Draconin Red

   https://doi.org/10.3390/molecules28083506  

   Solaris, Janak; Krueger, Taylor D.; Chen, Cheng; Fang, Chong (April 2023, Molecules)

   Proton transfer processes of organic molecules are key to charge transport and photoprotection in biological systems. Among them, excited-state intramolecular proton transfer (ESIPT) reactions are characterized by quick and efficient charge transfer within a molecule, resulting in ultrafast proton motions. The ESIPT-facilitated interconversion between two tautomers (PS and PA) comprising the tree fungal pigment Draconin Red in solution was investigated using a combination of targeted femtosecond transient absorption (fs-TA) and excited-state femtosecond stimulated Raman spectroscopy (ES-FSRS) measurements. Transient intensity (population and polarizability) and frequency (structural and cooling) dynamics of –COH rocking and –C=C, –C=O stretching modes following directed stimulation of each tautomer elucidate the excitation-dependent relaxation pathways, particularly the bidirectional ESIPT progression out of the Franck–Condon region to the lower-lying excited state, of the intrinsically heterogeneous chromophore in dichloromethane solvent. A characteristic overall excited-state PS-to-PA transition on the picosecond timescale leads to a unique “W”-shaped excited-state Raman intensity pattern due to dynamic resonance enhancement with the Raman pump–probe pulse pair. The ability to utilize quantum mechanics calculations in conjunction with steady-state electronic absorption and emission spectra to induce disparate excited-state populations in an inhomogeneous mixture of similar tautomers has broad implications for the modeling of potential energy surfaces and delineation of reaction mechanisms in naturally occurring chromophores. Such fundamental insights afforded by in-depth analysis of ultrafast spectroscopic datasets are also beneficial for future development of sustainable materials and optoelectronics. 

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3. Excited‐State Dynamics of a meta ‐Dimethylamino Locked GFP Chromophore as a Fluorescence Turn‐on Water Sensor ^†

   https://doi.org/10.1111/php.13552  

   Boulanger, Sean A.; Chen, Cheng; Myasnyanko, Ivan N.; Sokolov, Anatolii I.; Baranov, Mikhail S.; Fang, Chong (November 2021, Photochemistry and Photobiology)

   Abstract Strategic incorporation of ameta‐dimethylamino (–NMe₂) group on the conformationally locked green fluorescent protein (GFP) model chromophore (m‐NMe₂‐LpHBDI) has drastically altered molecular electronic properties, counterintuitively enhancing fluorescence of only the neutral and cationic chromophores in aqueous solution. A ~200‐fold decrease in fluorescence quantum yield ofm‐NMe₂‐LpHBDI in alcohols (e.g., MeOH, EtOH and 2‐PrOH) supports this GFP‐derived compound as a fluorescence turn‐on water sensor, with large fluorescence intensity differences between H₂O and ROH emissions in various H₂O/ROH binary mixtures. A combination of steady‐state electronic spectroscopy, femtosecond transient absorption, ground‐state femtosecond stimulated Raman spectroscopy (FSRS) and quantum calculations elucidates an intermolecular hydrogen‐bonding chain between a solvent –OH group and the chromophore phenolic ring –NMe₂and –OH functional groups, wherein fluorescence differences arise from an extended hydrogen‐bonding network beyond the first solvation shell, as opposed to fluorescence quenching via a dark twisted intramolecular charge‐transfer state. The absence of ameta‐NMe₂group twisting coordinate upon electronic excitation was corroborated by experiments on control samples without themeta‐NMe₂group or with bothmeta‐NMe₂andpara‐OH groups locked in a six‐membered ring. These deep mechanistic insights stemming from GFP chromophore scaffold will enable rational design of organic, compact and environmentally friendly water sensors. 

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4. Excited-state resonance Raman spectroscopy probes the sequential two-photon excitation mechanism of a photochromic molecular switch

   https://doi.org/10.1063/5.0126974  

   Burns, Kristen H.; Quincy, Timothy J.; Elles, Christopher G. (December 2022, The Journal of Chemical Physics)

   Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30 fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400 nm. Many of the modes that become enhanced in the 750 nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400 nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation. 

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5. Excited State Dynamics of 7-Deazaguanosine and Guanosine 5’-Monophosphate

   Krul, S. E.; Hoehn, S. J.; Feierabend, K.; Crespo-Hernández, C. E. (January 2021, ChemRxiv)

   null (Ed.)

   Minor structural modifications to the DNA and RNA nucleobases have a significant effect on their excited state dynamics and electronic relaxation pathways. In this study, the excited state dynamics of 7-deazaguanosine and guanosine 5′-monophosphate are investigated in aqueous solution and in a mixture of methanol and water using femtosecond broadband transient absorption spectroscopy following excitation at 267 nm. The transient spectra are collected using photon densities that ensure no parasitic multiphoton-induced signal from solvated electrons. The data can be fit satisfactorily using a two- or three-component kinetic model. By analyzing the results from steady-state, time-resolved, computational calculations, and the methanol–water mixture, the following general relaxation mechanism is proposed for both molecules, Lb → La → 1πσ*(ICT) → S0, where the 1πσ*(ICT) stands for an intramolecular charge transfer excited singlet state with significant πσ* character. In general, longer lifetimes for internal conversion are obtained for 7-deazaguanosine compared to guanosine 5′-monophosphate. Internal conversion of the 1πσ*(ICT) state to the ground state occurs on a similar time scale of a few picoseconds in both molecules. Collectively, the results demonstrate that substitution of a single nitrogen atom for a methine (C–H) group at position seven of the guanine moiety stabilizes the 1ππ* Lb and La states and alters the topology of their potential energy surfaces in such a way that the relaxation dynamics in 7-deazaguanosine are slowed down compared to those in guanosine 5′-monophosphate but not for the internal conversion of 1πσ*(ICT) state to the ground state. 

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