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Darari M, Domenichini E, Francés-Monerris A, et al. Iron(ii) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties. Dalton Trans. 2019;48(29):10915-10926doi: 10.1039/c9dt01731c.
Darari, M., Domenichini, E., Francés-Monerris, A., Cebrián, C., Magra, K., Beley, M., Pastore, M., Monari, A., Assfeld, X., Haacke, S., & Gros, P. C. (2019). Iron(ii) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties. Dalton transactions (Cambridge, England : 2003), 48(29), 10915-10926. https://doi.org/10.1039/c9dt01731c
Darari, Mohamed, et al. "Iron(ii) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties." Dalton transactions (Cambridge, England : 2003) vol. 48,29 (2019): 10915-10926. doi: https://doi.org/10.1039/c9dt01731c
Darari M, Domenichini E, Francés-Monerris A, Cebrián C, Magra K, Beley M, Pastore M, Monari A, Assfeld X, Haacke S, Gros PC. Iron(ii) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties. Dalton Trans. 2019 Aug 07;48(29):10915-10926. doi: 10.1039/c9dt01731c. Epub 2019 May 31. PMID: 31149683.
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Dalton Trans. 2019 Aug 07;48(29):10915-10926. doi: 10.1039/c9dt01731c. Epub 2019 May 31.

Iron(ii) complexes with diazinyl-NHC ligands: impact of π-deficiency of the azine core on photophysical properties.

Dalton transactions (Cambridge, England : 2003)

Mohamed Darari, Edoardo Domenichini, Antonio Francés-Monerris, Cristina Cebrián, Kevin Magra, Marc Beley, Mariachiara Pastore, Antonio Monari, Xavier Assfeld, Stefan Haacke, Philippe C Gros

Affiliations

  1. Université de Lorraine, CNRS, L2CM, F-54000 Nancy, France. [email protected].
  2. Université de Strasbourg, CNRS, IPCMS, F-67000 Strasbourg, France.
  3. Université de Lorraine, CNRS, LPCT, F-54000 Nancy, France.
  4. Université de Lorraine, CNRS, L2CM, F-57000 Metz, France.

PMID: 31149683 DOI: 10.1039/c9dt01731c

Abstract

Ligand field enhancing N-heterocyclic carbene (NHC) ligands were recently shown to prevent photo-induced spin crossover in Fe(ii) complexes due to their intricate effects on the electronic excited state structure. Due to their pico- to nanosecond lifetimes, these complexes are now good candidates for photo-sensitizing applications. Herein we report the synthesis and photophysical characterization of a new family of homoleptic Fe(ii) complexes with C^N^C ligands involving diazines as the central N-heteroaromatic ligand. For these four carbene bond complexes, ultrafast transient absorption spectroscopy revealed a significant improvement of the excited-state lifetime. A record 32 ps lifetime was measured for a complex bearing a ligand combining a π-deficient pyrazine nucleus and a benzimidazolylidene as NHC. When compared to other azine-based ligands investigated, we argue that the lifetimes are modulated by a small excited state barrier expressing the ability of the ligand to reach the Fe-N distance needed for internal conversion to the ground state.

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