Excitation-Wavelength-Dependent Photophysics of d8d8 Di-isocyanide Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00549946" target="_blank" >RIV/61388955:_____/22:00549946 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/22:43924236

Výsledek na webu

<a href="http://hdl.handle.net/11104/0325841" target="_blank" >http://hdl.handle.net/11104/0325841</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.1c02645" target="_blank" >10.1021/acs.inorgchem.1c02645</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Excitation-Wavelength-Dependent Photophysics of d8d8 Di-isocyanide Complexes

Popis výsledku v původním jazyce

Binuclear Rh(I) and Ir(I) TMB (2,5-dimethyl-2,5-diisocyanohexane) and dimen (1,8-diisocyanomenthane) complexes possess dσ*pσ and dπpσ singlet and triplet excited states that can be selectively excited in the visible and UV spectral regions. Using perturbational spin–orbit TDDFT, we unraveled the detailed character and spin mixing of these electronic transitions and found that delocalization of pσ and dπ orbitals over C≡N– groups makes C≡N stretching vibrations sensitive reporters of electron density and structural changes upon electronic excitation. Picosecond time-resolved infrared spectra measured after visible light, 375 nm, and 316 nm excitation revealed excitation-wavelength-dependent deactivation cascades. Visible light irradiation prepares the 1dσ*pσ state that, after one or two (sub)picosecond relaxation steps, undergoes 70–1300 ps intersystem crossing to 3dσ*pσ, which is faster for the more flexible dimen complexes. UV-excited 1,3dπpσ states decay with (sub)picosecond kinetics through a manifold of high-lying triplet and mixed-spin states to 3dσ*pσ with lifetimes in the range of 6–19 ps (316 nm) and 19–43 ps (375 nm, Ir only), bypassing 1dσ*pσ. Most excited-state conversion and some relaxation steps are accompanied by direct decay to the ground state that is especially pronounced for the most flexible long/eclipsed Rh(dimen) conformer.

Název v anglickém jazyce

Excitation-Wavelength-Dependent Photophysics of d8d8 Di-isocyanide Complexes

Popis výsledku anglicky

Binuclear Rh(I) and Ir(I) TMB (2,5-dimethyl-2,5-diisocyanohexane) and dimen (1,8-diisocyanomenthane) complexes possess dσ*pσ and dπpσ singlet and triplet excited states that can be selectively excited in the visible and UV spectral regions. Using perturbational spin–orbit TDDFT, we unraveled the detailed character and spin mixing of these electronic transitions and found that delocalization of pσ and dπ orbitals over C≡N– groups makes C≡N stretching vibrations sensitive reporters of electron density and structural changes upon electronic excitation. Picosecond time-resolved infrared spectra measured after visible light, 375 nm, and 316 nm excitation revealed excitation-wavelength-dependent deactivation cascades. Visible light irradiation prepares the 1dσ*pσ state that, after one or two (sub)picosecond relaxation steps, undergoes 70–1300 ps intersystem crossing to 3dσ*pσ, which is faster for the more flexible dimen complexes. UV-excited 1,3dπpσ states decay with (sub)picosecond kinetics through a manifold of high-lying triplet and mixed-spin states to 3dσ*pσ with lifetimes in the range of 6–19 ps (316 nm) and 19–43 ps (375 nm, Ir only), bypassing 1dσ*pσ. Most excited-state conversion and some relaxation steps are accompanied by direct decay to the ground state that is especially pronounced for the most flexible long/eclipsed Rh(dimen) conformer.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

61

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

2745-2759

Kód UT WoS článku

000732030300001

EID výsledku v databázi Scopus

2-s2.0-85121641950