The effects of symmetry and rigidity on non-adiabatic dynamics in tertiary amines:a time-resolved photoelectron velocity-map imaging study of the cage-amine ABCO

The non-adiabatic relaxation dynamics of the tertiary cage-amine azabicyclo[2.2.2]octane (ABCO, also known as quinuclidine) have been investigated following 3p Rydberg excitation at 201 nm using femtosecond time-resolved photoelectron imaging (TRPEI). The aim of the study was to investigate the influence of the rigid and symmetric cage structure found in ABCO on the general non-adiabatic relaxation processes commonly seen in other tertiary aliphatic amines (TAAs). Our data is compared with TRPEI results very recently obtained for several structurally less rigid TAA systems [J. O. F. Thompson et al., Chem. Sci., 2016, 7, 1826–1839] and helps to confirm many of the previously reported findings. The experimental results for ABCO in the short-time (<1 ps) regime strongly support earlier conclusions suggesting that planarization about the N-atom is not a prerequisite for efficient 3p–3s internal conversion. Additionally, individual photoelectron peaks within our ABCO data show no temporal shifts in energy. As confirmed by our supporting quantum mechanical calculations, this demonstrates that neither internal conversion within the 3p manifold or significant conformational re-organization are possible in the ABCO system. This result therefore lends strong additional support to the active presence of such dynamical effects in other, less conformationally restricted TAA species, where photoelectron peak shifts are commonly observed. Finally, the extremely long (>1 ns) 3s Rydberg state lifetime seen in ABCO (relative to other TAA systems at similar excitation energies) serves to illustrate the large influence of symmetry and conformational rigidity on intramolecular vibrational redistribution processes previously implicated in mediating this aspect of the overall relaxation dynamics

Guilty, innocent, or just molecules doing their thing? Structural, spectroscopic, and reactivity studies of iridium complexes with redox-active ligands

Advances in inorg. spectroscopy and theor. methods have spurred reevaluation of the electronic structures of many compds. comprising the canon of coordination chem. X-ray absorption (XAS) and ESR (EPR) spectroscopies, in concert with d. functional theory (DFT) calcns., have been of particular value in demonstrating that many classic ligands, such as 2, 2'-bipyridine, are redox-active. Such studies are less straightforward when directed at systems in which late, third-row metals are coordinated. This lecture will discuss electronic structure studies of [tris-(penatfluorophenylcorrole)]iridium bis-pyridine complexes and trismaleonitridiledithialato iridium complexes. Their electronic structures and redox chem. will be compared to cobalt and rhodium congeners. From these studies we affirm that, with high-valent iridium, covalency is the rule and thus redox is mol. - partitioning of redox events as "ligand-centered" or "metal-centered" inaccurately describes these systems