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

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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: and 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.

Original languageEnglish
Pages (from-to)11013-11022
Number of pages10
JournalNew Journal of Chemistry
Volume42
Issue number13
DOIs
Publication statusPublished - 1 Jan 2018

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Carbon Monoxide
Chromophores
Transition metals
Optical properties
Tuning
Actinoid Series Elements
Antennas
Electrons
Actinides
Chemical bonds
Coordination Complexes
Metal complexes
Discrete Fourier transforms
Orbits
Infrared radiation
Decomposition

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Cite this

@article{006efc5f45aa4a909709f295455345c6,
title = "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: and 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.",
author = "Plinio Cantero-L{\'o}pez and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez",
year = "2018",
month = "1",
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doi = "10.1039/c8nj00179k",
language = "English",
volume = "42",
pages = "11013--11022",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
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TY - JOUR

T1 - 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

AU - Cantero-López, Plinio

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

PY - 2018/1/1

Y1 - 2018/1/1

N2 - 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: and 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.

AB - 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: and 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.

UR - http://www.scopus.com/inward/record.url?scp=85049189141&partnerID=8YFLogxK

U2 - 10.1039/c8nj00179k

DO - 10.1039/c8nj00179k

M3 - Article

VL - 42

SP - 11013

EP - 11022

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 13

ER -