Počet záznamů: 1
Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction
- 1.
SYSNO ASEP 0584308 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction Tvůrce(i) Nemirovich, T. (CZ)
Young, B. (US)
Březina, K. (CZ)
Mason, P. E. (US)
Seidel, R. (DE)
Stemer, D. (DE)
Winter, B. (DE)
Jungwirth, P. (CZ)
Bradforth, S. E. (US)
Schewe, Hanns Christian (UFCH-W)Zdroj.dok. Journal of the American Chemical Society. - : American Chemical Society - ISSN 0002-7863
Roč. 146, č. 12 (2024), s. 8043-8057Poč.str. 15 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova generalized gradient approximation ; state perturbation-theory ; photoelectron-spectroscopy ; electronic-structure ; vibrational-spectra ; raman-spectra ; hartree-fock ; liquid water ; naphthalene ; benzene Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GA24-10982S GA ČR - Grantová agentura ČR Způsob publikování Open access Institucionální podpora UFCH-W - RVO:61388955 UT WOS 001166769300001 EID SCOPUS 85185787376 DOI 10.1021/jacs.3c11655 Anotace We investigate the electronic structure of aromatic radical anions in the solution phase employing a combination of liquid-jet (LJ) photoelectron (PE) spectroscopy measurements and electronic structure calculations. By using recently developed protocols, we accurately determine the vertical ionization energies of valence electrons of both the solvent and the solute molecules. In particular, we first characterize the pure solvent of tetrahydrofuran (THF) by LJ-PE measurements in conjunction with ab initio molecular dynamics simulations and G(0)W(0) calculations. Next, we determine the electronic structure of neutral naphthalene (Np) and benzophenone (Bp) as well as their radical anion counterparts Np- and Bp(-) in THF. Wherever feasible, we performed orbital assignments of the measured PE features of the aromatic radical anions, with comparisons to UV-vis absorption spectra of the corresponding neutral molecules being instrumental in rationalizing the assignments. Analysis of the electronic structure differences between the neutral species and their anionic counterparts provides understanding of the primarily electrostatic stabilization of the radical anions in solution. Finally, we obtain a very good agreement of the reduction potentials extracted from the present LJ-PES measurements of Np- and Bp(-) in THF with previous electrochemical data from cyclic voltammetry measurements. In this context, we discuss how the choice of solvent holds significant implications for optimizing conditions for the Birch reduction process, wherein aromatic radical anions play crucial roles as reactive intermediates. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2025 Elektronická adresa https://hdl.handle.net/11104/0352239
Počet záznamů: 1