4.5 Article

Influence of substituents in 1,10-phenanthroline on the structural and photophysical properties of W(CO)4(1,10-phenanthroline-type) complexes

Journal

INORGANICA CHIMICA ACTA
Volume 516, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2020.120166

Keywords

Tungsten complexes; Photoluminescence; Lifetime; Crystal structure; Supramolecular interactions

Funding

  1. postdoctoral FONDECYT grant [3180327]
  2. FONDECYT-Chile [1160749]
  3. CONICYT FONDEQUIP [EQM160099]
  4. Financiamiento Basal Proyecto (CEDENNA) [FB0807]

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This study investigates the impact of methyl and phenyl substituents in specific positions of the phen ligand on the structural and photophysical properties of [W(CO)(4)(phen-type)] complexes. The substituents significantly influence geometrical parameters, particularly the (OC)(eq)-W-(CO)(eq) angle, affecting the photophysical properties. The perturbation of the (OC)(eq)-W-(CO)(eq) angle induced by the substituents in the phen ligand plays a crucial role in determining the photophysical properties of these complexes.
In this work, methyl and phenyl substituents were introduced in the 2,9- and 4,7-positions of the phen ligand in order to study its impact on the structural and photophysical properties of [W(CO)(4)(phen-type)] complexes [phen-type = 4,7- dimethyl-1,10- phenanthroline (4,7-DMPhen); 4, 7-diphenyl-1,10-phenanthroline (BPhen), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (RCP)]. Crystallographic analysis of these complexes allows to investigate the correlation between the geometrical parameters with their photophysical properties measured by steady-state and time-resolved spectroscopies. The (OC)(eq)-W-(CO)(eq) angle is the most significantly influenced geometrical parameter by the substituents, showing values of 92.5 degrees, 90.2 degrees, and 81.2 degrees for [W(CO)(4)(4,7-DMPhen)], [W(CO)(4)(BPhen)], and [W(CO)(4)(BCP)], respectively. The smallest angle observed for [W(CO)(4)(BCP)] is attributed to a steric repulsion exerted by the methyl groups to the equatorial carbonyls. Remarkably, a smaller OCeq-W-COeq angle favors the High-Energy (HE) emission band, as evidenced in the photoluminescence (PL) spectra of [W(CO)(4)(BCP)]. Conversely, a greater angle favors the Low-Energy (LE) emission band, as observed in the PL spectra of [W(CO)(4)(4,7-DMPhen)] and [W(CO)(4)(BPhen)]. The PL lifetime of the LE emission band becomes shorter when decreasing the (OC)(eq)-W-(CO)(eq) angle. Furthermore, the absorption feature was affected by the 2,9-dimethyl substituents, showing greater contribution from the high-energy shoulder on the visible absorption band. This study shows that the perturbation of the (OC)(eq)-W-(CO)(eq) angle induced by the substituents in the phen ligand influences on the photophysical properties of [W(CO)(4)(phen-type)] complexes.

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