Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor

Vincent A. Corden, Anne K. Duhme-Klair, Sarah Hostachy, Robin N. Perutz, Nicole Reddig, Hans Christian Becker, Leif Hammarström

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A heteroditopic ligand H2-L consisting of a dihydroxybenzene (catechol)-unit linked via an amide bond to a pyridyl-unit and its methyl-protected precursor Me2-L were synthesized, characterized, and their photophysical properties investigated. The three accessible protonation states of the ligand, H2-L+, H2-L, and H-L-, showed distinct 1 H NMR, absorption and emission spectroscopic characteristics that allow pH-sensing. The spectroscopic signatures obtained act as a guide to understand the signaling mechanism of the luminescent pH and molybdate sensor [Re-(bpy)(CO)3(H2-L)]+. It was found that upon deprotonation of the 2-hydroxy group of H2-L, a ligand-based absorption band emerges that overlaps with the Re(dπ)-bpy metal-to-ligand charge transfer (MLCT) band of the sensor, reducing the quantum yield for emission on excitation in the 370 nm region. In addition, deprotonation of the catechol-unit leads to quenching of the emission from the Re(dn)→ bpy 3MLCT state, consistent with photoinduced electron transfer from the electron-rich, deprotonated catecholate to the Re-based luminophore. Finally, reaction of 2 equiv of [Re(bpy)(CO)3(H2-L)]+ with molybdate was shown to give the zwitterionic Mo(VI) complex [MoO2{Re(CO) 3-(bpy)(L)}2], as confirmed by electrospray ionization (ESI) mass spectrometry and X-ray crystallography. The crystal structure determination revealed that two fully deprotonated sensor molecules are bound via their oxygen-donors to a cis-dioxo-MoO2 center.

Original languageEnglish
Pages (from-to)1105-1115
Number of pages11
JournalInorganic Chemistry
Volume50
Issue number3
DOIs
Publication statusPublished - Feb 7 2011

Fingerprint

molybdates
Carbon Monoxide
Ligands
Deprotonation
ligands
sensors
Sensors
Electrospray ionization
Electrons
Protonation
X ray crystallography
Quantum yield
Amides
amides
crystallography
Mass spectrometry
Charge transfer
Absorption spectra
Quenching
electron transfer

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Corden, V. A., Duhme-Klair, A. K., Hostachy, S., Perutz, R. N., Reddig, N., Becker, H. C., & Hammarström, L. (2011). Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor. Inorganic Chemistry, 50(3), 1105-1115. https://doi.org/10.1021/ic1019422

Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor. / Corden, Vincent A.; Duhme-Klair, Anne K.; Hostachy, Sarah; Perutz, Robin N.; Reddig, Nicole; Becker, Hans Christian; Hammarström, Leif.

In: Inorganic Chemistry, Vol. 50, No. 3, 07.02.2011, p. 1105-1115.

Research output: Contribution to journalArticle

Corden, VA, Duhme-Klair, AK, Hostachy, S, Perutz, RN, Reddig, N, Becker, HC & Hammarström, L 2011, 'Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor', Inorganic Chemistry, vol. 50, no. 3, pp. 1105-1115. https://doi.org/10.1021/ic1019422
Corden VA, Duhme-Klair AK, Hostachy S, Perutz RN, Reddig N, Becker HC et al. Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor. Inorganic Chemistry. 2011 Feb 7;50(3):1105-1115. https://doi.org/10.1021/ic1019422
Corden, Vincent A. ; Duhme-Klair, Anne K. ; Hostachy, Sarah ; Perutz, Robin N. ; Reddig, Nicole ; Becker, Hans Christian ; Hammarström, Leif. / Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 3. pp. 1105-1115.
@article{2b635ef15ec440059945ed4b384bbce9,
title = "Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor",
abstract = "A heteroditopic ligand H2-L consisting of a dihydroxybenzene (catechol)-unit linked via an amide bond to a pyridyl-unit and its methyl-protected precursor Me2-L were synthesized, characterized, and their photophysical properties investigated. The three accessible protonation states of the ligand, H2-L+, H2-L, and H-L-, showed distinct 1 H NMR, absorption and emission spectroscopic characteristics that allow pH-sensing. The spectroscopic signatures obtained act as a guide to understand the signaling mechanism of the luminescent pH and molybdate sensor [Re-(bpy)(CO)3(H2-L)]+. It was found that upon deprotonation of the 2-hydroxy group of H2-L, a ligand-based absorption band emerges that overlaps with the Re(dπ)-bpy metal-to-ligand charge transfer (MLCT) band of the sensor, reducing the quantum yield for emission on excitation in the 370 nm region. In addition, deprotonation of the catechol-unit leads to quenching of the emission from the Re(dn)→ bpy 3MLCT state, consistent with photoinduced electron transfer from the electron-rich, deprotonated catecholate to the Re-based luminophore. Finally, reaction of 2 equiv of [Re(bpy)(CO)3(H2-L)]+ with molybdate was shown to give the zwitterionic Mo(VI) complex [MoO2{Re(CO) 3-(bpy)(L)}2], as confirmed by electrospray ionization (ESI) mass spectrometry and X-ray crystallography. The crystal structure determination revealed that two fully deprotonated sensor molecules are bound via their oxygen-donors to a cis-dioxo-MoO2 center.",
author = "Corden, {Vincent A.} and Duhme-Klair, {Anne K.} and Sarah Hostachy and Perutz, {Robin N.} and Nicole Reddig and Becker, {Hans Christian} and Leif Hammarstr{\"o}m",
year = "2011",
month = "2",
day = "7",
doi = "10.1021/ic1019422",
language = "English",
volume = "50",
pages = "1105--1115",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor

AU - Corden, Vincent A.

AU - Duhme-Klair, Anne K.

AU - Hostachy, Sarah

AU - Perutz, Robin N.

AU - Reddig, Nicole

AU - Becker, Hans Christian

AU - Hammarström, Leif

PY - 2011/2/7

Y1 - 2011/2/7

N2 - A heteroditopic ligand H2-L consisting of a dihydroxybenzene (catechol)-unit linked via an amide bond to a pyridyl-unit and its methyl-protected precursor Me2-L were synthesized, characterized, and their photophysical properties investigated. The three accessible protonation states of the ligand, H2-L+, H2-L, and H-L-, showed distinct 1 H NMR, absorption and emission spectroscopic characteristics that allow pH-sensing. The spectroscopic signatures obtained act as a guide to understand the signaling mechanism of the luminescent pH and molybdate sensor [Re-(bpy)(CO)3(H2-L)]+. It was found that upon deprotonation of the 2-hydroxy group of H2-L, a ligand-based absorption band emerges that overlaps with the Re(dπ)-bpy metal-to-ligand charge transfer (MLCT) band of the sensor, reducing the quantum yield for emission on excitation in the 370 nm region. In addition, deprotonation of the catechol-unit leads to quenching of the emission from the Re(dn)→ bpy 3MLCT state, consistent with photoinduced electron transfer from the electron-rich, deprotonated catecholate to the Re-based luminophore. Finally, reaction of 2 equiv of [Re(bpy)(CO)3(H2-L)]+ with molybdate was shown to give the zwitterionic Mo(VI) complex [MoO2{Re(CO) 3-(bpy)(L)}2], as confirmed by electrospray ionization (ESI) mass spectrometry and X-ray crystallography. The crystal structure determination revealed that two fully deprotonated sensor molecules are bound via their oxygen-donors to a cis-dioxo-MoO2 center.

AB - A heteroditopic ligand H2-L consisting of a dihydroxybenzene (catechol)-unit linked via an amide bond to a pyridyl-unit and its methyl-protected precursor Me2-L were synthesized, characterized, and their photophysical properties investigated. The three accessible protonation states of the ligand, H2-L+, H2-L, and H-L-, showed distinct 1 H NMR, absorption and emission spectroscopic characteristics that allow pH-sensing. The spectroscopic signatures obtained act as a guide to understand the signaling mechanism of the luminescent pH and molybdate sensor [Re-(bpy)(CO)3(H2-L)]+. It was found that upon deprotonation of the 2-hydroxy group of H2-L, a ligand-based absorption band emerges that overlaps with the Re(dπ)-bpy metal-to-ligand charge transfer (MLCT) band of the sensor, reducing the quantum yield for emission on excitation in the 370 nm region. In addition, deprotonation of the catechol-unit leads to quenching of the emission from the Re(dn)→ bpy 3MLCT state, consistent with photoinduced electron transfer from the electron-rich, deprotonated catecholate to the Re-based luminophore. Finally, reaction of 2 equiv of [Re(bpy)(CO)3(H2-L)]+ with molybdate was shown to give the zwitterionic Mo(VI) complex [MoO2{Re(CO) 3-(bpy)(L)}2], as confirmed by electrospray ionization (ESI) mass spectrometry and X-ray crystallography. The crystal structure determination revealed that two fully deprotonated sensor molecules are bound via their oxygen-donors to a cis-dioxo-MoO2 center.

UR - http://www.scopus.com/inward/record.url?scp=79951605707&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79951605707&partnerID=8YFLogxK

U2 - 10.1021/ic1019422

DO - 10.1021/ic1019422

M3 - Article

C2 - 21218777

AN - SCOPUS:79951605707

VL - 50

SP - 1105

EP - 1115

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 3

ER -