Characterization of diarylethene-based photoswitches with core and valence photoabsorption and photoemission spectroscopies
Abstract
We investigate the electronic structure of two dithienylethene (DTE) molecular photoswitches, BTF6 and PTF6, in the gas phase by combining valence photoelectron spectroscopy (PES), x-ray photoelectron spectroscopy, and the near-edge x-ray absorption fine structure. DTEs have attracted significant attention due to their high photoisomerization quantum yield, fatigue resistance, and thermal irreversibility, which underpin applications ranging from molecular machines to photoswitchable biomolecules. Supported by first-principles simulations, our analysis elucidates how the different extent of π-conjugation, arising from the distinct thiophene/benzothiophene subunits, manifests across the various spectroscopic observables. By comparing the calculated signatures of the open- and closed-ring isomers, we further assess the sensitivity of each probe to the structural changes associated with photoinduced cyclization. Overall, these results deliver a detailed picture of the intrinsic electronic properties of DTEs in the gas phase and provide a robust basis for future time-resolved studies of their ultrafast photoisomerization dynamics.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (19)
M. Pini
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
S. Severino
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
L. Mai
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
L. Colaizzi
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
M. Alagia
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC, Area Science Park Basovizza 1 , Trieste,
O. Plekan
Elettra-Sincrotrone Trieste 3 , Strada Statale 14 - km 163,5 in AREA Science Park, 34149 Basovizza, Trieste,
R. Richter
Elettra-Sincrotrone Trieste 3 , Strada Statale 14 - km 163,5 in AREA Science Park, 34149 Basovizza, Trieste,
E. Arfaoui
Universitá di Bologna - Alma Mater Studiorum, Dipartimento di Chimica Industriale “Toso Montanari 4 ,” Via Piero Gobetti 85, 40129 Bologna,
F. Montorsi
Università di Bologna—Alma Mater Studiorum 2 , Via Piero Gobetti 85, 40129 Bologna,
F. Segatta
Universitá di Bologna - Alma Mater Studiorum, Dipartimento di Chimica Industriale “Toso Montanari 4 ,” Via Piero Gobetti 85, 40129 Bologna,
M. Garavelli
Universitá di Bologna - Alma Mater Studiorum, Dipartimento di Chimica Industriale “Toso Montanari 4 ,” Via Piero Gobetti 85, 40129 Bologna,
S. Aloïse
LASIRE - Laboratoire de Spectroscopie pour les Interactions, la Réactivité et l’Environnement, Université de Lille, CNRS 5 , UMR 8516, 59500 Lille,
L. Poisson
Université Paris-Saclay, ISMO, CNRS 6 , Rue André Rivière, 91400 Orsay,
R. Borrego-Varillas
CNR, Istituto di Fotonica e Nanotecnologie 7 , Piazza Leonardo da Vinci 32, 20133 Milan,
M. Lucchini
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
M. Coreno
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC 2 , Area Science Park Basovizza, Trieste,
M. Nisoli
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
M. Reduzzi
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
A. Nenov
Department of Industrial Chemistry “Toso Montanari,” University of Bologna 3 , Via Piero Gobetti 86, Bologna 40129,