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Spectroscopic and s...
Spectroscopic and structural investigations reveal the signaling mechanism of a luminescent molybdate sensor
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- Corden, V.A. (författare)
- University of York
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- Duhme-Klair, A-K. (författare)
- University of York
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- Hostachy, S. (författare)
- University of York
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- Perutz, R.N. (författare)
- University of York
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- Redding, N. (författare)
- University of York
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- Becker, Hans-Christian, 1971 (författare)
- Uppsala universitet,Kemisk fysik
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- Hammarström, Leif (författare)
- Uppsala universitet,Kemisk fysik
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(creator_code:org_t)
- 2011-01-10
- 2011
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 50:3, s. 1105-1115
- Relaterad länk:
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http://dx.doi.org/10...
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https://research.cha...
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https://doi.org/10.1...
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https://urn.kb.se/re...
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Abstract
Ämnesord
Stäng
- 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 2-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(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(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.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
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