Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents

Abstract

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Direct observation ofo-benzyne formation in photochemical hexadehydro-Diels–Alder (hν-HDDA) reactions

“…Although quantitative dynamics of bimolecular reactions in solution have been extensively reported for other species, the precondition for these studies is that only one of the reactants can be excited by the pump pulses. [101][102][103][104][105][106] Thus, we limit our analysis to a qualitative discussion due to the existence of both excited bis-diynes and excited perylene.…”

Charge-transfer and impulsive electronic-to-vibrational energy conversion in ferricyanide: ultrafast photoelectron and transient infrared studies

“…The fundamental of the CN radical stretch vibration is expected near 2050 cm −1 , 44 but its extinction coefficient is almost two orders of magnitude weaker than that of ferricyanide. As a result, CN radicals have not even been detected in transient IR experiments, even when they were produced with high quantum yield by photodissociation of ICN 45 . Due to the low efficiency of ferricyanide dissociation and spectral overlap with Fe(CN) 6 ions, it may also be difficult to identify the cyanide radicals in transient visible spectra, where they were shown to give rise to a rather broad band centred at 385 nm, shifting to shorter wavelengths during solvation 46 .…”

Photochemical reaction dynamics of 2,2′-dithiobis(benzothiazole): direct observation of the addition product of an aromatic thiyl radical to an alkene with time-resolved vibrational and electronic absorption spectroscopy

“…Given that the time constants for these two bands match the second component of the decay of the BS radical in styrene solution obtained by TEAS and TVAS, they are assigned to the product of the BS radical addition reaction with styrene. This product is proposed to be the anti-Markovnikov type addition product, BS-St radical formed through reaction scheme (6).…”