Lanthanide appended rotaxanes respond to changing chloride concentration

Clemence Allain; Paul D. Beer; Stephen Faulkner; Michael W. Jones; Alan M.  Kenwright; Nathan L. Kilah; Richard C. Knighton; Thomas Just Sørensen; Manuel Tropiano

doi:10.1039/c2sc21614k

Lanthanide appended rotaxanes respond to changing chloride concentration

Clemence Allain, Paul D. Beer, Stephen Faulkner, Michael W. Jones, Alan M. Kenwright, Nathan L. Kilah, Richard C. Knighton, Thomas Just Sørensen, Manuel Tropiano

34 Citations (Scopus)

Abstract

Lanthanide appended rotaxanes have been prepared by the CuAAC 'click' reaction between an azide appended rotaxane and lanthanide complexes of propargyl DO3A. The resulting complexes are luminescent, and exhibit chloride responsive luminescence behavior consistent with the existence of two independent halide binding pockets, one in the rotaxane cavity and one on the ninth (axial) coordination site of the lanthanide. Strong halide binding to europium gives rise to changes in the relative intensity of the hypersensitive ΔJ = 2 transition compared to the rest of the europium emission spectrum, combined with quenching of the overall intensity of emission as a consequence of non-radiative quenching by the bound halide. The weaker interaction with the rotaxane pocket mediates a subsequent recovery of intensity of the europium centered luminescence despite the considerable separation between the lanthanide and the rotaxane binding pocket.

Original language	English
Journal	Chemical Science
Volume	4
Issue number	1
Pages (from-to)	489-493
ISSN	2041-6520
DOIs	https://doi.org/10.1039/c2sc21614k
Publication status	Published - 2013
Externally published	Yes

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title = "Lanthanide appended rotaxanes respond to changing chloride concentration",

abstract = "Lanthanide appended rotaxanes have been prepared by the CuAAC 'click' reaction between an azide appended rotaxane and lanthanide complexes of propargyl DO3A. The resulting complexes are luminescent, and exhibit chloride responsive luminescence behavior consistent with the existence of two independent halide binding pockets, one in the rotaxane cavity and one on the ninth (axial) coordination site of the lanthanide. Strong halide binding to europium gives rise to changes in the relative intensity of the hypersensitive ΔJ = 2 transition compared to the rest of the europium emission spectrum, combined with quenching of the overall intensity of emission as a consequence of non-radiative quenching by the bound halide. The weaker interaction with the rotaxane pocket mediates a subsequent recovery of intensity of the europium centered luminescence despite the considerable separation between the lanthanide and the rotaxane binding pocket.",

author = "Clemence Allain and Beer, {Paul D.} and Stephen Faulkner and Jones, {Michael W.} and Kenwright, {Alan M.} and Kilah, {Nathan L.} and Knighton, {Richard C.} and S{\o}rensen, {Thomas Just} and Manuel Tropiano",

year = "2013",

doi = "10.1039/c2sc21614k",

language = "English",

volume = "4",

pages = "489--493",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Lanthanide appended rotaxanes respond to changing chloride concentration

AU - Allain, Clemence

AU - Beer, Paul D.

AU - Faulkner, Stephen

AU - Jones, Michael W.

AU - Kenwright, Alan M.

AU - Kilah, Nathan L.

AU - Knighton, Richard C.

AU - Sørensen, Thomas Just

AU - Tropiano, Manuel

PY - 2013

Y1 - 2013

N2 - Lanthanide appended rotaxanes have been prepared by the CuAAC 'click' reaction between an azide appended rotaxane and lanthanide complexes of propargyl DO3A. The resulting complexes are luminescent, and exhibit chloride responsive luminescence behavior consistent with the existence of two independent halide binding pockets, one in the rotaxane cavity and one on the ninth (axial) coordination site of the lanthanide. Strong halide binding to europium gives rise to changes in the relative intensity of the hypersensitive ΔJ = 2 transition compared to the rest of the europium emission spectrum, combined with quenching of the overall intensity of emission as a consequence of non-radiative quenching by the bound halide. The weaker interaction with the rotaxane pocket mediates a subsequent recovery of intensity of the europium centered luminescence despite the considerable separation between the lanthanide and the rotaxane binding pocket.

AB - Lanthanide appended rotaxanes have been prepared by the CuAAC 'click' reaction between an azide appended rotaxane and lanthanide complexes of propargyl DO3A. The resulting complexes are luminescent, and exhibit chloride responsive luminescence behavior consistent with the existence of two independent halide binding pockets, one in the rotaxane cavity and one on the ninth (axial) coordination site of the lanthanide. Strong halide binding to europium gives rise to changes in the relative intensity of the hypersensitive ΔJ = 2 transition compared to the rest of the europium emission spectrum, combined with quenching of the overall intensity of emission as a consequence of non-radiative quenching by the bound halide. The weaker interaction with the rotaxane pocket mediates a subsequent recovery of intensity of the europium centered luminescence despite the considerable separation between the lanthanide and the rotaxane binding pocket.

U2 - 10.1039/c2sc21614k

DO - 10.1039/c2sc21614k

M3 - Journal article

SN - 2041-6520

VL - 4

SP - 489

EP - 493

JO - Chemical Science

JF - Chemical Science

IS - 1

ER -

Lanthanide appended rotaxanes respond to changing chloride concentration

Abstract

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