Photochemistry of Rh(CO)2(acetylacetonate) and Related Metal Dicarbonyls Studied by Ultrafast Infrared Spectroscopy

Computational Modelling of Nanoporous Materials

“…The computational modelling, however, suggested that this band should be assigned to rhodium carbonyl species which contain additional hydrogen ligands, for example, Rh(CO)(H 2 ) þ or Rh(CO)(H) 2 þ , whereas the zeolite supported complex Rh(CO) þ is characterized by the IR band observed at 2014 cm À1 , 77 with a frequency shift relative to dicarbonyl similar to the experimental IR shift of the corresponding molecular Rh þ carbonyl complexes. 79 These corrected assignments were later confirmed experimentally. 80 Ivanova et al 81 reported combined experimental IR and computational study of CO, NO, and mixed CO/NO complexes of Rh þ and Rh 2þ located in ZSM-5 zeolite.…”

Transient 2D-IR spectroscopy of inorganic excited states

“…71 A second application of the same FT-2D-IR methodology was used to probe the orientational relaxation of a similar system following photodissociation. 72 The Mn 2 (CO) 10 dimer was used to generate two Mn(CO) 5 species with 2D-IR used to measure the rotation time as a function of time following excitation. In this case it was shown that orientational dynamics became progressively slower as the time following excitation increased.…”

“…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.…”

Excited state properties of (acetylacetonato)dicarbonyliridium(I)

“…Owing to the presence of the strong-field ligand CO an interference by low-energy ligand field (LF) states may be avoided. Indeed, it is known that in contrast to Rh I (CO) 2 acac, our target complex is much less light sensitive [10,11]. In the Rh(I) complex reactive LF states are apparently low enough to dominate the excited state behavior of the complex [12].…”