TY - JOUR
T1 - The role of the excited state dynamic of the antenna ligand in the lanthanide sensitization mechanism
AU - Beltrán-Leiva, María Joaquina
AU - Solis-Céspedes, Eduardo
AU - Páez-Hernández, Dayán
N1 - Funding Information:
This work has been supported by the Grant FONDECYT No. 1180017.
PY - 2020/6/14
Y1 - 2020/6/14
N2 - A fragmentation scheme combined with a series of theoretical approximations like TD-DFT, and multiconfigurational CASSCF/NEVPT2 methods, has been used to describe the photophysical phenomena associated with the antenna effect and lanthanide ion emission. The theoretical protocol was used in (Cp2Ph)3Tb and (Cp2Ph)TbCl2(THF)3, where Cp2Ph= diphenylcyclopentadienyl and THF = tetrahydrofuran, organometallic complexes recently reported by Roitershteinet al.(Inorg. Chem., 2018,57, 10199) The excited-state dynamic of the antenna ligand shows an important vibronic coupling associated with the radiative and non-radiative process with rate constants in the order normally reported for organic molecules. The methodology proposed herein allows a justification of the back-energy transfer observed experimentally in the (Cp2Ph)3Tb complex and the efficient energy transfer mechanism in (Cp2Ph)TbCl2(THF)3, thus proving to be a robust tool in the determination of the sensitization pathways in organometallic lanthanide complexes.
AB - A fragmentation scheme combined with a series of theoretical approximations like TD-DFT, and multiconfigurational CASSCF/NEVPT2 methods, has been used to describe the photophysical phenomena associated with the antenna effect and lanthanide ion emission. The theoretical protocol was used in (Cp2Ph)3Tb and (Cp2Ph)TbCl2(THF)3, where Cp2Ph= diphenylcyclopentadienyl and THF = tetrahydrofuran, organometallic complexes recently reported by Roitershteinet al.(Inorg. Chem., 2018,57, 10199) The excited-state dynamic of the antenna ligand shows an important vibronic coupling associated with the radiative and non-radiative process with rate constants in the order normally reported for organic molecules. The methodology proposed herein allows a justification of the back-energy transfer observed experimentally in the (Cp2Ph)3Tb complex and the efficient energy transfer mechanism in (Cp2Ph)TbCl2(THF)3, thus proving to be a robust tool in the determination of the sensitization pathways in organometallic lanthanide complexes.
UR - http://www.scopus.com/inward/record.url?scp=85086281976&partnerID=8YFLogxK
U2 - 10.1039/d0dt01132k
DO - 10.1039/d0dt01132k
M3 - Article
C2 - 32432635
AN - SCOPUS:85086281976
SN - 1477-9226
VL - 49
SP - 7444
EP - 7450
JO - Dalton Transactions
JF - Dalton Transactions
IS - 22
ER -