(IL)-I-1 and (MLCT)-M-3 excited states modulated by H+: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl) pyrazine)Re(CO)(3)Br]: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br]

Nancy Pizarro, Marianela Saldías, Nicolás Guzmán, Catalina Sandoval-Altamirano, Samia Kahlal, Jean Yves Saillard, Jean René Hamon, Andrés Vega

Resultado de la investigación: Article

1 Cita (Scopus)

Resumen

The reaction of 2-bromo-5-(1H-pyrazol-1-yl)pyrazine (LI) and bromotricarbonyl(tetrahydrofuran)-rhenium(i) dimer leads to the monometallic complex [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br] (I), which displays a non-regular octahedral geometry around the ReI center, a fac-correlation for carbonyls, with the pyrazine and pyrazolyl rings being highly coplanar. I experiences one irreversible oxidation at Ep,a = 1.067 V and two irreversible reductions at Ep,c = −1.445 V and −1.675 V. DFT supports that the oxidation is a metal-centered process but the first reduction wave should be a ligand-centered process. Comparison with related complexes suggests that the second reduction is metal centered (ReI/Re0). Three absorption bands were observed for I around 260, 315 and 400 nm, and the first two were assigned to the intraligand (IL) π → π* transitions while the band around 400 nm corresponds to a metal-to-ligand charge transfer (MLCT) transition. Excitation of I at 280 nm leads to two emission bands at 360 nm and 640 nm, and the first one is attributed to the 1IL transition and the second to 3MLCT. The 3MLCT emission decays with lifetimes of 17 and 44 ns in MeCN and DCM, respectively. Addition of trifluoroacetic acid to the solution leads to its reaction with the 3MLCT excited state, giving rise to a long-lived and very oxygen sensitive species, 3ILH+. This behaviour makes I a potential sensor for protons and possibly other cations in solution.

Idioma originalEnglish
Páginas (desde-hasta)2449-2457
Número de páginas9
PublicaciónNew Journal of Chemistry
Volumen43
N.º6
DOI
EstadoPublished - 14 feb 2019

Huella dactilar

Pyrazines
Carbon Monoxide
Excited states
Charge transfer
Metals
Ligands
Rhenium
Trifluoroacetic acid
Trifluoroacetic Acid
Oxidation
Discrete Fourier transforms
Dimers
Cations
Protons
Absorption spectra
Positive ions
Oxygen
Geometry
Sensors

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

Citar esto

@article{cc6c4cdd50114ecab6af9a913a169f81,
title = "(IL)-I-1 and (MLCT)-M-3 excited states modulated by H+: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl) pyrazine)Re(CO)(3)Br]: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br]",
abstract = "The reaction of 2-bromo-5-(1H-pyrazol-1-yl)pyrazine (LI) and bromotricarbonyl(tetrahydrofuran)-rhenium(i) dimer leads to the monometallic complex [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br] (I), which displays a non-regular octahedral geometry around the ReI center, a fac-correlation for carbonyls, with the pyrazine and pyrazolyl rings being highly coplanar. I experiences one irreversible oxidation at Ep,a = 1.067 V and two irreversible reductions at Ep,c = −1.445 V and −1.675 V. DFT supports that the oxidation is a metal-centered process but the first reduction wave should be a ligand-centered process. Comparison with related complexes suggests that the second reduction is metal centered (ReI/Re0). Three absorption bands were observed for I around 260, 315 and 400 nm, and the first two were assigned to the intraligand (IL) π → π* transitions while the band around 400 nm corresponds to a metal-to-ligand charge transfer (MLCT) transition. Excitation of I at 280 nm leads to two emission bands at 360 nm and 640 nm, and the first one is attributed to the 1IL transition and the second to 3MLCT. The 3MLCT emission decays with lifetimes of 17 and 44 ns in MeCN and DCM, respectively. Addition of trifluoroacetic acid to the solution leads to its reaction with the 3MLCT excited state, giving rise to a long-lived and very oxygen sensitive species, 3ILH+. This behaviour makes I a potential sensor for protons and possibly other cations in solution.",
author = "Nancy Pizarro and Marianela Sald{\'i}as and Nicol{\'a}s Guzm{\'a}n and Catalina Sandoval-Altamirano and Samia Kahlal and Saillard, {Jean Yves} and Hamon, {Jean Ren{\'e}} and Andr{\'e}s Vega",
year = "2019",
month = "2",
day = "14",
doi = "10.1039/c8nj04196b",
language = "English",
volume = "43",
pages = "2449--2457",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "6",

}

(IL)-I-1 and (MLCT)-M-3 excited states modulated by H+: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl) pyrazine)Re(CO)(3)Br] : the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br]. / Pizarro, Nancy; Saldías, Marianela; Guzmán, Nicolás; Sandoval-Altamirano, Catalina; Kahlal, Samia; Saillard, Jean Yves; Hamon, Jean René; Vega, Andrés.

En: New Journal of Chemistry, Vol. 43, N.º 6, 14.02.2019, p. 2449-2457.

Resultado de la investigación: Article

TY - JOUR

T1 - (IL)-I-1 and (MLCT)-M-3 excited states modulated by H+: the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl) pyrazine)Re(CO)(3)Br]

T2 - the structure and photophysical properties of [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br]

AU - Pizarro, Nancy

AU - Saldías, Marianela

AU - Guzmán, Nicolás

AU - Sandoval-Altamirano, Catalina

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Hamon, Jean René

AU - Vega, Andrés

PY - 2019/2/14

Y1 - 2019/2/14

N2 - The reaction of 2-bromo-5-(1H-pyrazol-1-yl)pyrazine (LI) and bromotricarbonyl(tetrahydrofuran)-rhenium(i) dimer leads to the monometallic complex [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br] (I), which displays a non-regular octahedral geometry around the ReI center, a fac-correlation for carbonyls, with the pyrazine and pyrazolyl rings being highly coplanar. I experiences one irreversible oxidation at Ep,a = 1.067 V and two irreversible reductions at Ep,c = −1.445 V and −1.675 V. DFT supports that the oxidation is a metal-centered process but the first reduction wave should be a ligand-centered process. Comparison with related complexes suggests that the second reduction is metal centered (ReI/Re0). Three absorption bands were observed for I around 260, 315 and 400 nm, and the first two were assigned to the intraligand (IL) π → π* transitions while the band around 400 nm corresponds to a metal-to-ligand charge transfer (MLCT) transition. Excitation of I at 280 nm leads to two emission bands at 360 nm and 640 nm, and the first one is attributed to the 1IL transition and the second to 3MLCT. The 3MLCT emission decays with lifetimes of 17 and 44 ns in MeCN and DCM, respectively. Addition of trifluoroacetic acid to the solution leads to its reaction with the 3MLCT excited state, giving rise to a long-lived and very oxygen sensitive species, 3ILH+. This behaviour makes I a potential sensor for protons and possibly other cations in solution.

AB - The reaction of 2-bromo-5-(1H-pyrazol-1-yl)pyrazine (LI) and bromotricarbonyl(tetrahydrofuran)-rhenium(i) dimer leads to the monometallic complex [(2-bromo-5-(1H-pyrazol-1-yl)pyrazine)Re(CO)3Br] (I), which displays a non-regular octahedral geometry around the ReI center, a fac-correlation for carbonyls, with the pyrazine and pyrazolyl rings being highly coplanar. I experiences one irreversible oxidation at Ep,a = 1.067 V and two irreversible reductions at Ep,c = −1.445 V and −1.675 V. DFT supports that the oxidation is a metal-centered process but the first reduction wave should be a ligand-centered process. Comparison with related complexes suggests that the second reduction is metal centered (ReI/Re0). Three absorption bands were observed for I around 260, 315 and 400 nm, and the first two were assigned to the intraligand (IL) π → π* transitions while the band around 400 nm corresponds to a metal-to-ligand charge transfer (MLCT) transition. Excitation of I at 280 nm leads to two emission bands at 360 nm and 640 nm, and the first one is attributed to the 1IL transition and the second to 3MLCT. The 3MLCT emission decays with lifetimes of 17 and 44 ns in MeCN and DCM, respectively. Addition of trifluoroacetic acid to the solution leads to its reaction with the 3MLCT excited state, giving rise to a long-lived and very oxygen sensitive species, 3ILH+. This behaviour makes I a potential sensor for protons and possibly other cations in solution.

UR - http://www.scopus.com/inward/record.url?scp=85061162023&partnerID=8YFLogxK

U2 - 10.1039/c8nj04196b

DO - 10.1039/c8nj04196b

M3 - Article

AN - SCOPUS:85061162023

VL - 43

SP - 2449

EP - 2457

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 6

ER -