The ligand-to-metal charge transfer excited state of [Re(dmpe)3]2+

Electronic Structure and Photophysics of Low Spin d5 Metallocenes

“…The vibrational fine structure known for this complex is not conveyed within its calculated absorption spectra as only electronic excitations were calculated. Interestingly, both low energy transitions exhibit 99% LMCT character, uncharacteristic of previously reported rhenium­(II) complexes where metal–ligand mixing is more prevalent. , Solvatochromism was similarly not observed for this complex across four solvents (dielectric constants ranging from 1.8–8.9), − further supporting the presence of highly symmetric LMCT excited states (Figures S5 and S6). …”

“…Interestingly, both low energy transitions exhibit 99% LMCT character, uncharacteristic of previously reported rhenium­(II) complexes where metal–ligand mixing is more prevalent. , Solvatochromism was similarly not observed for this complex across four solvents (dielectric constants ranging from 1.8–8.9), − further supporting the presence of highly symmetric LMCT excited states (Figures S5 and S6). …”

“…51,52 Solvatochromism was similarly not observed for this complex across four solvents (dielectric constants ranging from 1.8−8.9), 53−55 further supporting the presence of highly symmetric LMCT excited states (Figures S5 and S6). 52 The optical transitions that dominate the UV−vis absorption spectrum of MnCp* 2 are similar to those quantified for ReCp* 2 (Figure 5A). The lowest energy absorption feature at 468 nm is attributed to two excited states (13 and 14), consisting of electron transfer from Cp*(π)-based molecular orbitals (MO 79β and 80β) to a Mn d-orbital (MO 83β).…”

Luminescent First-Row Transition Metal Complexes

“…On the one hand, this includes comparatively abundant second- and third-row transition metals (for example Zr, , Mo, ,,, or W ,,,, ) or f-elements (for example Ce , ). On the other hand, molecular complexes of abundant main group elements are now attracting increasing attention as luminophores and provide additional insight into how nonradiative relaxation can be tamed. − At the same time, further developments of precious metal-based complexes (for example, Ru, ,, Rh, , Re, − Ir, − or Pt − ) have significantly advanced the field of inorganic photophysics and photochemistry. Regardless of whether complexes of d-, f-, or main group elements are considered, the interplay between synthetic, spectroscopic, and computational work seems crucial for the development of new designer luminophores.…”

A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions

“…It also further underscores the opportunity to leverage TD-DFT to help identify and visualize the ligand-based orbitals that participate in LMCT transitions, and gain a deeper understanding of the ligand properties needed to support low energy LMCT excited states. 22,47,55,[63][64][65] The d electron congurations for complexes with LMCT excited states are also diverse. In particular, d 0 complexes are well known for low-lying LMCT excited states, resulting from their vacant metal orbitals which can easily be populated by lled ligand orbitals.…”