Vibrational energy redistribution in Cp*Ir(CO)2 (Cp*=η5-pentamethylcyclopentadienyl) studied by broadband transient infrared spectroscopy

Investigating the vibrational dynamics of a 17e−metallocarbonyl intermediate using ultrafast two dimensional infrared spectroscopy

“…The value obtained for the vibrational population relaxation time (T 1 ) of 1 is somewhat faster than typically observed via this approach for monomeric metal carbonyl derivatives. 55 It is noteworthy however that the dimetallic nature of this compound will lead to a significant increase in the number of vibrational degrees of freedom and a concomitant increase in the number of possible pathways for intramolecular vibrational relaxation. As such, the decreased T 1 time is unsurprising.…”

“…However, biexponential decay profiles have been observed for several metallocarbonyl systems similar to those observed for 1 here and assigned to a combination of inter-CO IVR and population relaxation. 42,55,57 As such, given the established trend of strong vibrational interaction between carbonyl-stretching modes, it would be remarkable indeed if similar dynamics were not occurring in the transient species, given the close chemical similarity to the parent species.…”

The role of CN and CO ligands in the vibrational relaxation dynamics of model compounds of the [FeFe]-hydrogenase enzyme

“…17 These observations are consistent with a number of studies using both 2D-IR methods and other ultrafast techniques to study the vibrational relaxation of metal carbonyls in solution. [13][14][15][18][19][20][21][22][23][24][25][26][27] In this article, ultrafast 2D-IR methods have been applied to study the spectroscopy and vibrational dynamics of [NEt 4 + ] 2 (m-propanedithiolate)Fe 2 (CO) 4 (CN) 2 2À , 1, in dichloromethane (DCM) solution. This model system takes a further step toward accurately mimicking the [FeFe] active site by the incorporation of two cyano ligands.…”

Transient 2D-IR spectroscopy of inorganic excited states

“…The introduction of time-resolved spectroscopy methods, employing an IR probe of an electronically-excited system, opened up further possibilities for following photochemical processes or dynamics associated with, or subsequent to, excitation. [1][2][3][4][5][6][7][8][9][10] Implementation of these techniques has progressed in line with laser technology development to the extent that spectrometers with high time resolution (~50 fs) and broad spectral bandwidths (>300 cm -1 ) are readily achievable using commercially-available bench-top laser systems. As chemical research in the inorganic sector advances and the molecules become more complex, the need arises to understand, and so eventually control, their excited state chemistry and dynamics at ever more nuanced levels.…”