2022
DOI: 10.1002/bkcs.12495
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Photodissociation dynamics of chlorobenzene and 4‐fluoroiodobenzene in CCl4 probed using time‐resolved infrared spectroscopy

Abstract: The dynamics of photoexcited chlorobenzene (PhCl) and 4-fluoroiodobenzne (4-FPhI) in CCl 4 were investigated using time-resolved infrared spectroscopy. When excited at 267 nm, 50% (70%) of the excited PhCl (4-FPhI) dissociates the Cl (I) atom immediately, and the remaining molecules relax into the T 1 state via intersystem crossing (ISC) with a time constant of 70-80 ps. About half of the dissociated halogen atoms geminately recombine with the nascent radical with a time constant of 100-150 ps, reducing the nu… Show more

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Cited by 4 publications
(5 citation statements)
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“…Details of the TR spectrometer have been described elsewhere. 17 In short, an intense 800 nm pulse with a repetition rate of 1 kHz from a Ti:sapphire amplifier pumped two optical parametric amplifiers (OPAs), [18][19][20][21][22] which generated a visible pump pulse and a mid-IR probe pulse. Frequency doubling of a signal pulse from one OPA generated a 3 μJ visible pump pulse at 575 nm, and difference frequency mixing of the signal and idler pulses from the other OPA produced a tunable mid-IR probe pulse.…”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…Details of the TR spectrometer have been described elsewhere. 17 In short, an intense 800 nm pulse with a repetition rate of 1 kHz from a Ti:sapphire amplifier pumped two optical parametric amplifiers (OPAs), [18][19][20][21][22] which generated a visible pump pulse and a mid-IR probe pulse. Frequency doubling of a signal pulse from one OPA generated a 3 μJ visible pump pulse at 575 nm, and difference frequency mixing of the signal and idler pulses from the other OPA produced a tunable mid-IR probe pulse.…”
Section: Methodsmentioning
confidence: 99%
“…Details of the TR spectrometer have been described elsewhere 17 . In short, an intense 800 nm pulse with a repetition rate of 1 kHz from a Ti:sapphire amplifier pumped two optical parametric amplifiers (OPAs), 18–22 which generated a visible pump pulse and a mid‐IR probe pulse.…”
Section: Methodsmentioning
confidence: 99%
“… 28 , 34 In cyclohexane solution, the fluorescence lifetime of the chlorobenzene S 1 state is similar, and the lifetime of the T 1 (ππ*) state was measured to be about 1 μs using phosphorescence and transient absorption spectroscopy. 25 , 35 The shorter (∼80 ps) S 1 -state lifetime reported by Park et al for chlorobenzene photoexcited at 267 nm in CCl 4 solution 36 could be because of excited-state electron-transfer reactions with the chlorinated solvent.…”
Section: Introductionmentioning
confidence: 95%
“…Chlorinated solvents are avoided because of possible electron-transfer reactions with PhCl (S 1 ) and because they show their own photochemistry when subjected to ultrafast UV laser pulses. 36 , 46 − 49 …”
Section: Introductionmentioning
confidence: 99%
“…Thus, MLCT and LMCT (ligand-to-metal charge-transfer) excited states composed of earth-abundant metal elements have merited increasing attention. [24][25][26][27][28][29][30][31][32][33][34][35][36][37] In particular, the absence of any possible d-d transitions in the d 10 configuration has made Cu(I) complexes quite interesting for MLCT emitters and photoredox catalysts, which have been well studied and reviewed. [38][39][40][41][42][43][44][45][46][47][48][49][50] This review focuses on redox reactivity of MLCT and LMCT excited states of earth-abundant metal complexes, such as iron, manganese, cobalt, and chromium complexes, together with the lifetimes and redox potentials of the MLCT and LMCT excited states, which are different depending on metals, ligands, and Lewis acids bound to ligands (e.g., oxygen atom of the metal-oxo moiety).…”
Section: Introductionmentioning
confidence: 99%