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

doi:10.1016/j.poly.2012.02.030

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 journal › Article › peer-review

Abstract

[Ru(bpy)₃]²⁺ complexes derivatized with two aminoethylglycine (aeg) chains bearing pendant bipyridine ligands coordinate Zn²⁺ 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 Zn²⁺ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn²⁺ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy)₃]²⁺ core that are closest to the Zn²⁺. 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 language	English (US)
Pages (from-to)	118-124
Number of pages	7
Journal	Polyhedron
Volume	40
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2012.02.030
State	Published - Jun 19 2012

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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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 Zn2+ 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 Zn2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy)3]2+ core that are closest to the Zn2+. 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.",

author = "Myers, {Carl P.} and Sha Sun and Showalter, {Scott A.} and Miller, {James R.} and Williams, {Mary Elizabeth}",

year = "2012",

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

AU - Myers, Carl P.

AU - Sun, Sha

AU - Showalter, Scott A.

AU - Miller, James R.

AU - Williams, Mary Elizabeth

PY - 2012/6/19

Y1 - 2012/6/19

N2 - [Ru(bpy)3]2+ complexes derivatized with two aminoethylglycine (aeg) chains bearing pendant bipyridine ligands coordinate Zn2+ 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 Zn2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy)3]2+ core that are closest to the Zn2+. 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 Zn2+ 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 Zn2+ is added. Using spectral assignments from 1 and 2D NMR spectra, the spectrophotometric titrations reveal that Zn2+ binding causes significant shifts of the peaks assigned to the protons on the [Ru(bpy)3]2+ core that are closest to the Zn2+. 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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JO - Polyhedron

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ER -

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

Abstract

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