The Selectivity of Water-based Pyrophosphate Recognition is Tuned by Metal Substitution in Dimetallic Receptors

Simon  Svane; Frank Kjeldsen; Vickie McKee; Christine McKenzie

doi:10.1039/c5dt00729a

The Selectivity of Water-based Pyrophosphate Recognition is Tuned by Metal Substitution in Dimetallic Receptors

Simon Svane, Frank Kjeldsen, Vickie McKee, Christine McKenzie

University of Southern Denmark

Research output: Contribution to journal › Journal article › Research › peer-review

Abstract

The three dimetallic compounds [Ga ₂(bpbp)(OH) ₂(H ₂O) ₂](ClO ₄) ₃, [In ₂(bpbp)(CH ₃CO ₂) ₂](ClO ₄) ₃ and [Zn ₂(bpbp)(HCO ₂) ₂](ClO ₄) (bpbp ^- = 2,6-bis((N,N′-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate) were evaluated as stable solid state precursors for reactive solution state receptors to use for the recognition of the biologically important anion pyrophosphate in water at neutral pH. Indicator displacement assays using in situ generated complex-pyrocatechol violet adducts, {M ₂(bpbp)(H _xPV)} ⁿ⁺ M = Ga ³⁺, In ³⁺, Zn ²⁺, were tested for selectivity in their reactions with a series of common anions: pyrophosphate, phosphate, ATP, arsenate, nitrate, perchlorate, chloride, sulfate, formate, carbonate and acetate. The receptor employing Ga ³⁺ showed a slow but visually detectable response (blue to yellow) in the presence of one equivalent of pyrophosphate but no response to any other anion, even when they were present in much higher concentrations. The systems based on In ³⁺ or Zn ²⁺ show less selectivity in accord with visibly discernible responses to several of the anions. These results demonstrate a facile method for increasing anion selectivity without modification of an organic dinucleating ligand scaffold. The comfortable supramolecular recognition of pyrophosphate by the dimetallic complexes is demonstrated by the single crystal X-ray structure of [Ga ₂(bpbp)(HP ₂O ₇)](ClO ₄) ₂ in which the pyrophosphate is coordinated to the two gallium ions via four of its oxygen atoms.

Original language	English
Journal	Dalton Transactions
Volume	44
Issue number	26
Pages (from-to)	11877-11886
ISSN	1477-9226
DOIs	https://doi.org/10.1039/c5dt00729a
Publication status	Published - 2015

Keywords

Colorimetry
Crystallography, X-Ray
Diphosphates/analysis
Gallium/chemistry
Indium/chemistry
Ligands
Models, Molecular
Organometallic Compounds/chemistry
Spectrophotometry, Ultraviolet
Water/analysis
Zinc/chemistry

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title = "The Selectivity of Water-based Pyrophosphate Recognition is Tuned by Metal Substitution in Dimetallic Receptors",

abstract = "The three dimetallic compounds [Ga 2(bpbp)(OH) 2(H 2O) 2](ClO 4) 3, [In 2(bpbp)(CH 3CO 2) 2](ClO 4) 3 and [Zn 2(bpbp)(HCO 2) 2](ClO 4) (bpbp - = 2,6-bis((N,N′-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate) were evaluated as stable solid state precursors for reactive solution state receptors to use for the recognition of the biologically important anion pyrophosphate in water at neutral pH. Indicator displacement assays using in situ generated complex-pyrocatechol violet adducts, {M 2(bpbp)(H xPV)} n+ M = Ga 3+, In 3+, Zn 2+, were tested for selectivity in their reactions with a series of common anions: pyrophosphate, phosphate, ATP, arsenate, nitrate, perchlorate, chloride, sulfate, formate, carbonate and acetate. The receptor employing Ga 3+ showed a slow but visually detectable response (blue to yellow) in the presence of one equivalent of pyrophosphate but no response to any other anion, even when they were present in much higher concentrations. The systems based on In 3+ or Zn 2+ show less selectivity in accord with visibly discernible responses to several of the anions. These results demonstrate a facile method for increasing anion selectivity without modification of an organic dinucleating ligand scaffold. The comfortable supramolecular recognition of pyrophosphate by the dimetallic complexes is demonstrated by the single crystal X-ray structure of [Ga 2(bpbp)(HP 2O 7)](ClO 4) 2 in which the pyrophosphate is coordinated to the two gallium ions via four of its oxygen atoms.",

keywords = "Colorimetry, Crystallography, X-Ray, Diphosphates/analysis, Gallium/chemistry, Indium/chemistry, Ligands, Models, Molecular, Organometallic Compounds/chemistry, Spectrophotometry, Ultraviolet, Water/analysis, Zinc/chemistry",

author = "Simon Svane and Frank Kjeldsen and Vickie McKee and Christine McKenzie",

year = "2015",

doi = "10.1039/c5dt00729a",

language = "English",

volume = "44",

pages = "11877--11886",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "26",

}

TY - JOUR

T1 - The Selectivity of Water-based Pyrophosphate Recognition is Tuned by Metal Substitution in Dimetallic Receptors

AU - Svane, Simon

AU - Kjeldsen, Frank

AU - McKee, Vickie

AU - McKenzie, Christine

PY - 2015

Y1 - 2015

N2 - The three dimetallic compounds [Ga 2(bpbp)(OH) 2(H 2O) 2](ClO 4) 3, [In 2(bpbp)(CH 3CO 2) 2](ClO 4) 3 and [Zn 2(bpbp)(HCO 2) 2](ClO 4) (bpbp - = 2,6-bis((N,N′-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate) were evaluated as stable solid state precursors for reactive solution state receptors to use for the recognition of the biologically important anion pyrophosphate in water at neutral pH. Indicator displacement assays using in situ generated complex-pyrocatechol violet adducts, {M 2(bpbp)(H xPV)} n+ M = Ga 3+, In 3+, Zn 2+, were tested for selectivity in their reactions with a series of common anions: pyrophosphate, phosphate, ATP, arsenate, nitrate, perchlorate, chloride, sulfate, formate, carbonate and acetate. The receptor employing Ga 3+ showed a slow but visually detectable response (blue to yellow) in the presence of one equivalent of pyrophosphate but no response to any other anion, even when they were present in much higher concentrations. The systems based on In 3+ or Zn 2+ show less selectivity in accord with visibly discernible responses to several of the anions. These results demonstrate a facile method for increasing anion selectivity without modification of an organic dinucleating ligand scaffold. The comfortable supramolecular recognition of pyrophosphate by the dimetallic complexes is demonstrated by the single crystal X-ray structure of [Ga 2(bpbp)(HP 2O 7)](ClO 4) 2 in which the pyrophosphate is coordinated to the two gallium ions via four of its oxygen atoms.

AB - The three dimetallic compounds [Ga 2(bpbp)(OH) 2(H 2O) 2](ClO 4) 3, [In 2(bpbp)(CH 3CO 2) 2](ClO 4) 3 and [Zn 2(bpbp)(HCO 2) 2](ClO 4) (bpbp - = 2,6-bis((N,N′-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate) were evaluated as stable solid state precursors for reactive solution state receptors to use for the recognition of the biologically important anion pyrophosphate in water at neutral pH. Indicator displacement assays using in situ generated complex-pyrocatechol violet adducts, {M 2(bpbp)(H xPV)} n+ M = Ga 3+, In 3+, Zn 2+, were tested for selectivity in their reactions with a series of common anions: pyrophosphate, phosphate, ATP, arsenate, nitrate, perchlorate, chloride, sulfate, formate, carbonate and acetate. The receptor employing Ga 3+ showed a slow but visually detectable response (blue to yellow) in the presence of one equivalent of pyrophosphate but no response to any other anion, even when they were present in much higher concentrations. The systems based on In 3+ or Zn 2+ show less selectivity in accord with visibly discernible responses to several of the anions. These results demonstrate a facile method for increasing anion selectivity without modification of an organic dinucleating ligand scaffold. The comfortable supramolecular recognition of pyrophosphate by the dimetallic complexes is demonstrated by the single crystal X-ray structure of [Ga 2(bpbp)(HP 2O 7)](ClO 4) 2 in which the pyrophosphate is coordinated to the two gallium ions via four of its oxygen atoms.

KW - Colorimetry

KW - Crystallography, X-Ray

KW - Diphosphates/analysis

KW - Gallium/chemistry

KW - Indium/chemistry

KW - Ligands

KW - Models, Molecular

KW - Organometallic Compounds/chemistry

KW - Spectrophotometry, Ultraviolet

KW - Water/analysis

KW - Zinc/chemistry

U2 - 10.1039/c5dt00729a

DO - 10.1039/c5dt00729a

M3 - Journal article

C2 - 26057368

SN - 1477-9226

VL - 44

SP - 11877

EP - 11886

JO - Dalton Transactions

JF - Dalton Transactions

IS - 26

ER -

The Selectivity of Water-based Pyrophosphate Recognition is Tuned by Metal Substitution in Dimetallic Receptors

Abstract

Keywords

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