The emission spectrum of ruthenocene: calculation of the excited-state distortions and the spacings in the repetitive pattern

A comparison of ground- and excited-state properties of gas phase and crystalline ruthenocene using density functional theory

“…One question addressed by these authors, and to which they found no satisfactory answer, is the fact that this doubling is not found in absorption. In their paper, Hollingsworth et al 4 pointed out that there is evidence in the well-resolved structure of the emission spectrum for appreciable displacements of the potentials of the ground and excited states along another vibrational mode than the totally symmetric one. In order to fit the experimental spectrum quantitatively, they invoked additional displacements along the two ring-tilt modes at 381 and 400 cm Ϫ1 , respectively, and along the asymmetric Ru-cp stretch at 445 cm Ϫ1 .…”

“…The concomitant increase in metal-ring bond lengths can be verified spectroscopically by the observation of a Stokes shift of around 10 000 cm Ϫ1 and a long progression in the totally symmetric metal-ring stretch vibration in the emission spectrum of Ru͑cp͒ 2 in the solid state. [3][4][5] Previously, Daul et al 6 presented the results of density functional ͑DF͒ calculations on the excited-state energies, multiplet splittings and excited-state distortions along the metal-ring stretch of ruthenocene, performed with the DEMON 7 program package. The overall agreement between the calculations and the spectroscopic properties was very good.…”

“…However, the comparatively simple model with only the totally symmetric metal-ring stretch as active vibration fails to account for some intriguing spectroscopic features. Hollingsworth et al 4 noticed progressions in other than the totally symmetric metal-ring stretch vibration, indicating substantial excited-state distortions along bending coordinates, and Riesen et al 5 noted an absence of mirror symmetry in the fine structure between absorption and emission.…”

Optical properties of bis(cyclopentadienyl)magnesium: excimer-type luminescence of the bis(cyclopentadienyl) ligand frame

“…In this case the ligand-ligand interaction is based on the (Cp À ) 3 fragment. Other metallocenes such as RuCp 2 [20][21][22][23][24][25] and OsCp 2 [26] exhibit also a phosphorescence. However, this emission originates from dd triplets which are apparently located below the intraligand states.…”

Laser-Induced Fluorescence of Rhenocene in Low-Temperature Matrixes: Selective Excitation and Emission

“…Apart from our own work, there have been two groups of studies of emission from cyclopentadienyl complexes, both reporting extensive vibrational fine structure. The emission of ruthenocene in the solid state has been assigned to a spinforbidden ligand-field transition: [12][13][14][15] copper mount (ca. 40°to vertical).…”