Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)4 2+

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F17%3A00481864" target="_blank" >RIV/61388955:_____/17:00481864 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/17:43914021

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.jpca.7b10215" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.7b10215</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.7b10215" target="_blank" >10.1021/acs.jpca.7b10215</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)4 2+

Popis výsledku v původním jazyce

Binuclear complexes of d(8) metals (Pt-II, Ir-I, Rh-I,) exhibit diverse photonic behavior, including dual emission from relatively long-lived singlet and triplet excited states, as well as photochemical energy, electron, and atom transfer. Time-resolved optical spectroscopic and X-ray studies have revealed the behavior of the dimetallic core, confirming that M-M bonding is strengthened upon d sigma* -> p sigma excitation. We report the bridging ligand dynamics of Ir-2(1,8-diisocyanomenthane)(4)(2+) (Ir(dimen)), investigated by fs-ns time-resolved IR spectroscopy (TRIR) in the region of C N stretching vibrations, nu(C N), 2000-2300 cm(-1). The nu(C N) IR band of the singlet and triplet d sigma*p sigma excited states is shifted by -22 and -16 cm(-1) relative to the ground state due to delocalization of the p sigma LUMO over the bridging ligands. Ultrafast relaxation dynamics of the (1)d sigma*p sigma state depend on the initially excited Franck-Condon molecular geometry, whereby the same relaxed singlet excited state is populated by two different pathways depending on the starting point at the excited-state potential energy surface. Exciting the long/eclipsed isomer triggers two-stage structural relaxation: 0.5 ps large-scale Ir-Ir contraction and 5 ps Ir-Ir contraction/intramolecular rotation. Exciting the short/twisted isomer induces a similar to 5 ps bond shortening combined with vibrational cooling. Intersystem crossing (70 ps) follows, populating a 3d sigma*p sigma state that lives for hundreds of nanoseconds. During the first 2 ps, the nu(C N) IR bandwidth oscillates with the frequency of the nu(Ir-Ir) wave packet, ca. 80 cm(-1), indicating that the dephasing time of the high-frequency (16 fs)(-1) C N stretch responds to much slower (similar to 400 fs)(-1) Ir-Ir coherent oscillations.

Název v anglickém jazyce

Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)4 2+

Popis výsledku anglicky

Binuclear complexes of d(8) metals (Pt-II, Ir-I, Rh-I,) exhibit diverse photonic behavior, including dual emission from relatively long-lived singlet and triplet excited states, as well as photochemical energy, electron, and atom transfer. Time-resolved optical spectroscopic and X-ray studies have revealed the behavior of the dimetallic core, confirming that M-M bonding is strengthened upon d sigma* -> p sigma excitation. We report the bridging ligand dynamics of Ir-2(1,8-diisocyanomenthane)(4)(2+) (Ir(dimen)), investigated by fs-ns time-resolved IR spectroscopy (TRIR) in the region of C N stretching vibrations, nu(C N), 2000-2300 cm(-1). The nu(C N) IR band of the singlet and triplet d sigma*p sigma excited states is shifted by -22 and -16 cm(-1) relative to the ground state due to delocalization of the p sigma LUMO over the bridging ligands. Ultrafast relaxation dynamics of the (1)d sigma*p sigma state depend on the initially excited Franck-Condon molecular geometry, whereby the same relaxed singlet excited state is populated by two different pathways depending on the starting point at the excited-state potential energy surface. Exciting the long/eclipsed isomer triggers two-stage structural relaxation: 0.5 ps large-scale Ir-Ir contraction and 5 ps Ir-Ir contraction/intramolecular rotation. Exciting the short/twisted isomer induces a similar to 5 ps bond shortening combined with vibrational cooling. Intersystem crossing (70 ps) follows, populating a 3d sigma*p sigma state that lives for hundreds of nanoseconds. During the first 2 ps, the nu(C N) IR bandwidth oscillates with the frequency of the nu(Ir-Ir) wave packet, ca. 80 cm(-1), indicating that the dephasing time of the high-frequency (16 fs)(-1) C N stretch responds to much slower (similar to 400 fs)(-1) Ir-Ir coherent oscillations.

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

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

121

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

9275-9283

Kód UT WoS článku

000417672000011

EID výsledku v databázi Scopus

2-s2.0-85037740393