Characterization of the hemithioindigo photoswitch and its derivatives with x-ray photoabsorption and photoemission spectroscopies
Abstract
In this study, we investigate the electronic structure of hemithioindigo–hemistilbene (HTI) photoswitches and their functionalized derivatives, HTI-OMe and HTI-SMe, using x-ray photoemission spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. HTI compounds are known for their high quantum yield, thermal bistability, and rapid photoisomerization, making them promising candidates for applications in molecular motors, optical materials, and photocatalysis. Our analysis, supported by first-principles simulations, reveals how the conjugation of heteroatoms within the π-system affects the core-level chemical shifts and ionization intensities in XPS, while NEXAFS probes the influence of substituents on virtual molecular orbitals and energy transitions. In particular, the comparison between different functionalized HTIs allowed us to evaluate the effect of electronic relaxation following core-level photoionization and photo-excitation. These results provide a detailed understanding of the influence of functionalization on the electron distribution of HTI compounds, providing a robust foundation for the study and control of ultrafast charge transfer and photoswitching mechanisms in these molecular systems.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (26)
L. Oberti
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
L. Avaldi
CNR, Istituto di Struttura della Materia, Sede Secondaria di Montelibretti 4 , Area della Ricerca di Roma 1, Monterotondo Scalo,
P. Bolognesi
CNR, Istituto di Struttura della Materia, Sede Secondaria di Montelibretti 4 , Area della Ricerca di Roma 1, Monterotondo Scalo,
M. Bonanomi
R. Borrego-Varillas
CNR, Istituto di Fotonica e Nanotecnologie 7 , Piazza Leonardo da Vinci 32, 20133 Milan,
C. Callegari
Elettra-Sincrotrone Trieste 5 , Strada Statale 14—km 163.5, in AREA Science Park, IT-34149 Basovizza, Trieste,
L. Carlini
CNR, Istituto di Struttura della Materia, Sede Secondaria di Montelibretti 4 , Area della Ricerca di Roma 1, Monterotondo Scalo,
J. Chiarinelli
CNR, Istituto di Struttura della Materia, Sede Secondaria di Montelibretti 4 , Area della Ricerca di Roma 1, Monterotondo Scalo,
E. Ciekalski
Friedrich-Alexander-Universität Erlangen-Nürnberg Department of Chemistry and Pharmacy 6 , Nikolaus-Fiebiger-Str. 10, 91058 Erlangen,
M. Coreno
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC 2 , Area Science Park Basovizza, Trieste,
M. Devetta
CNR, Istituto di Fotonica e Nanotecnologie 2 , Piazza Leonardo da Vinci 32, 20133 Milan,
M. Di Fraia
Elettra-Sincrotrone Trieste 5 , Strada Statale 14—km 163.5, in AREA Science Park, IT-34149 Basovizza, Trieste,
M. Garavelli
Universitá di Bologna - Alma Mater Studiorum, Dipartimento di Chimica Industriale “Toso Montanari 4 ,” Via Piero Gobetti 85, 40129 Bologna,
M. Goffe
Università di Bologna—Alma Mater Studiorum, Dipartimento di Chimica Industriale ”Toso Montanari,” 8 Via Piero Gobetti 85, 40129 Bologna,
C. Grazioli
Elettra-Sincrotrone Trieste 5 , Strada Statale 14—km 163.5, in AREA Science Park, IT-34149 Basovizza, Trieste,
F. Montorsi
Università di Bologna—Alma Mater Studiorum 2 , Via Piero Gobetti 85, 40129 Bologna,
K. C. Prince
Elettra-Sincrotrone Trieste 5 , Strada Statale 14—km 163.5, in AREA Science Park, IT-34149 Basovizza, Trieste,
R. Richter
Elettra-Sincrotrone Trieste 3 , Strada Statale 14 - km 163,5 in AREA Science Park, 34149 Basovizza, Trieste,
F. Segatta
Universitá di Bologna - Alma Mater Studiorum, Dipartimento di Chimica Industriale “Toso Montanari 4 ,” Via Piero Gobetti 85, 40129 Bologna,
S. Waldmannstetter
Friedrich-Alexander-Universität Erlangen-Nürnberg Department of Chemistry and Pharmacy 6 , Nikolaus-Fiebiger-Str. 10, 91058 Erlangen,
G. Cerullo
Politecnico di Milano, Physics Department 1 , Piazza Leonardo da Vinci 32, 20133 Milan,
H. Dube
Friedrich-Alexander-Universität Erlangen-Nürnberg Department of Chemistry and Pharmacy 6 , Nikolaus-Fiebiger-Str. 10, 91058 Erlangen,
O. Plekan
Elettra-Sincrotrone Trieste 3 , Strada Statale 14 - km 163,5 in AREA Science Park, 34149 Basovizza, Trieste,
D. Faccialà
CNR, Istituto di Fotonica e Nanotecnologie 2 , Piazza Leonardo da Vinci 32, 20133 Milan,
C. Vozzi
CNR, Istituto di Fotonica e Nanotecnologie 2 , 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,