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Spectroscopic and Structural Investigations Reveal the Signaling Mechanism of a Luminescent Molybdate Sensor
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2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 3, 1105-1115 p.Article in journal (Refereed) Published
Abstract [en]

A heteroditopic ligand H(2)-L consisting of a dihydroxybenzene (catechol)-unit linked via an amide bond to a pyridyl-unit and its methyl-protected precursor Me(2)-L were synthesized, characterized, and their photophysical properties investigated. The three accessible protonation states of the ligand, H(3)-L(+), H(2)-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)(H(2)-L)](+). It was found that upon deprotonation of the 2-hydroxy group of H(2)-L, a ligand-based absorption band emerges that overlaps with the Re(d pi)-> 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(d pi)-> bpy (3)MLCT 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)(H(2)-L)](+) with molybdate was shown to give the zwitterionic Mo(VI) complex [MoO(2){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-MoO(2) center.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2011. Vol. 50, no 3, 1105-1115 p.
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Physical Chemistry
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URN: urn:nbn:se:uu:diva-166114DOI: 10.1021/ic1019422ISI: 000286688700052OAI: oai:DiVA.org:uu-166114DiVA: diva2:476198
Available from: 2012-01-11 Created: 2012-01-10 Last updated: 2017-12-08Bibliographically approved

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Hammarström, Leif

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