Issue 13, 2018

Tuning the molecular antenna effect using donor and acceptor substituents on the optical properties of the [(C5F5)2ThMCp2]2+ and [(C5F5)2ThMCpL2]+ complexes, where M = Fe, Ru and Os and L = CO and C5H5N

Abstract

In the present work, a theoretical methodology based on DFT is used to establish the effects of the electron rearrangements on the optical properties in a series of unsupported Th–M (transition metal) complexes of the form: Image ID:c8nj00179k-t1.gif and Image ID:c8nj00179k-t2.gif where Cp = C5H5, Cp′′ = C5F5, L = CO, C5H5N (py) and TM = Fe, Ru, Os. The role of the [MCp(L)2] chromophore is determined using different theoretical approaches like Morokuma–Ziegler energy decomposition analysis combined with the Extended Transition State with Natural Orbitals of Chemical Valence (ETS-NOCV). An important electron-donation and back-donation synergic interaction was found, which determines the degree of covalence of the chemical bond. Finally, the spin–orbit-ZORA calculation shows the possible Near Infra-Red (NIR) emission induced by the transition metal chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

Graphical abstract: Tuning the molecular antenna effect using donor and acceptor substituents on the optical properties of the [(C5F5)2ThMCp2]2+ and [(C5F5)2ThMCpL2]+ complexes, where M = Fe, Ru and Os and L = CO and C5H5N

Supplementary files

Article information

Article type
Paper
Submitted
11 Jan 2018
Accepted
20 May 2018
First published
21 May 2018

New J. Chem., 2018,42, 11013-11022

Tuning the molecular antenna effect using donor and acceptor substituents on the optical properties of the [(C5F5)2ThMCp2]2+ and [(C5F5)2ThMCpL2]+ complexes, where M = Fe, Ru and Os and L = CO and C5H5N

P. Cantero-López, D. Páez-Hernández and R. Arratia-Pérez, New J. Chem., 2018, 42, 11013 DOI: 10.1039/C8NJ00179K

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