NMR investigations of the solution structures of Ru-Zn complexes tethered by oligo(aminoethylglycine) chains

Carl P. Myers, Sha Sun, Scott A. Showalter, James R. Miller, Mary Elizabeth Williams

Research output: Contribution to journalArticle

Abstract

[Ru(bpy) 3] 2+ complexes derivatized with two aminoethylglycine (aeg) chains bearing pendant bipyridine ligands coordinate Zn 2+ to form a coordinative interchain crosslink. Although [Zn(bpy) 2] 2+ is both redox and spectroscopically silent, when bound to [Ru(bpy) 3] 2+ by the aeg strands it causes quenching of the emissive Ru complex excited state. 1H NMR spectroscopy is used to monitor changes in the structure and environment of the Ru complex during a titration as Zn 2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn 2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy) 3] 2+ core that are closest to the Zn 2+. These shifts reveal changes in the local environment that are likely a combination of electrostatic interactions between the two dication metal complexes and strain induced by the metal ion crosslinking the strands.

Original languageEnglish (US)
Pages (from-to)118-124
Number of pages7
JournalPolyhedron
Volume40
Issue number1
DOIs
StatePublished - Jun 19 2012

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Titration
titration
strands
Bearings (structural)
Nuclear magnetic resonance
nuclear magnetic resonance
causes
shift
crosslinking
Metal complexes
Coulomb interactions
Excited states
Crosslinking
Nuclear magnetic resonance spectroscopy
Metal ions
Quenching
metal ions
Protons
quenching
Coordination Complexes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "NMR investigations of the solution structures of Ru-Zn complexes tethered by oligo(aminoethylglycine) chains",
abstract = "[Ru(bpy) 3] 2+ complexes derivatized with two aminoethylglycine (aeg) chains bearing pendant bipyridine ligands coordinate Zn 2+ to form a coordinative interchain crosslink. Although [Zn(bpy) 2] 2+ is both redox and spectroscopically silent, when bound to [Ru(bpy) 3] 2+ by the aeg strands it causes quenching of the emissive Ru complex excited state. 1H NMR spectroscopy is used to monitor changes in the structure and environment of the Ru complex during a titration as Zn 2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn 2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy) 3] 2+ core that are closest to the Zn 2+. These shifts reveal changes in the local environment that are likely a combination of electrostatic interactions between the two dication metal complexes and strain induced by the metal ion crosslinking the strands.",
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NMR investigations of the solution structures of Ru-Zn complexes tethered by oligo(aminoethylglycine) chains. / Myers, Carl P.; Sun, Sha; Showalter, Scott A.; Miller, James R.; Williams, Mary Elizabeth.

In: Polyhedron, Vol. 40, No. 1, 19.06.2012, p. 118-124.

Research output: Contribution to journalArticle

TY - JOUR

T1 - NMR investigations of the solution structures of Ru-Zn complexes tethered by oligo(aminoethylglycine) chains

AU - Myers, Carl P.

AU - Sun, Sha

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N2 - [Ru(bpy) 3] 2+ complexes derivatized with two aminoethylglycine (aeg) chains bearing pendant bipyridine ligands coordinate Zn 2+ to form a coordinative interchain crosslink. Although [Zn(bpy) 2] 2+ is both redox and spectroscopically silent, when bound to [Ru(bpy) 3] 2+ by the aeg strands it causes quenching of the emissive Ru complex excited state. 1H NMR spectroscopy is used to monitor changes in the structure and environment of the Ru complex during a titration as Zn 2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn 2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy) 3] 2+ core that are closest to the Zn 2+. These shifts reveal changes in the local environment that are likely a combination of electrostatic interactions between the two dication metal complexes and strain induced by the metal ion crosslinking the strands.

AB - [Ru(bpy) 3] 2+ complexes derivatized with two aminoethylglycine (aeg) chains bearing pendant bipyridine ligands coordinate Zn 2+ to form a coordinative interchain crosslink. Although [Zn(bpy) 2] 2+ is both redox and spectroscopically silent, when bound to [Ru(bpy) 3] 2+ by the aeg strands it causes quenching of the emissive Ru complex excited state. 1H NMR spectroscopy is used to monitor changes in the structure and environment of the Ru complex during a titration as Zn 2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn 2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy) 3] 2+ core that are closest to the Zn 2+. These shifts reveal changes in the local environment that are likely a combination of electrostatic interactions between the two dication metal complexes and strain induced by the metal ion crosslinking the strands.

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