Compounds and Methods for Enhancing Metal Luminescence that Can be Selectively Turned Off
AssigneeQueen's University at Kingston
InventorsSuning Wang, Maria Vartan, Barry A. Blight, Larissa Frances Smith, Hee-Jun Park
Life of this patent
Estimating the term…
Abstract
Organoboron ligands have been reacted with rare earth metal ions to form complexes. These ligands enhance the metal ion's luminescence, wherein enhancement of luminescence can be turned off selectively by the presence of fluoride or cyanide and luminescence at a different wavelength is turned on. Methods of detection of fluoride, cyanide and biological markers are described.
Claims49
A method of enhancing luminescence of rare earth metal ions comprising:
- reacting rare earth metal ions with a triarylboron ligand to form a complex;
- and
- irradiating the complex with UV light,
- wherein the triarylboron ligand comprises (a) a binding portion and (b) a boron atom that is bound to three aryl moieties such that there are six positions of the aryl moieties that are ortho to the boron and the boron is sterically encumbered by substituents at two or more of the six ortho positions, wherein (i) at least two substituents at the six ortho positions comprise two or more carbons or (ii) at least four substituents at the six ortho positions are C1.
A method of detecting fluoride, cyanide or a biological marker comprising:
- contacting a test solution that potentially comprises fluoride, cyanide or a biological marker with a medium comprising a triarylboron bound-rare earth metal complex;
- irradiating the medium with UV light;
- and
- determining whether luminescence is produced at the wavelength of the ligand's fluorescence thereby indicating the presence of fluoride, cyanide or a biological marker, or whether luminescence is produced at the wavelength of the metal ion's emission indicating the absence of fluoride, cyanide or a biological marker;
- wherein the triarylboron bound-rare earth metal complex comprises a triarylboron ligand, which comprises a boron bound to three aryl moieties having a total of six ortho positions relative to the boron, and the boron is sterically encumbered by substituents that are located at two or more of the six ortho positions, wherein (i) at least two of the six ortho positions are independently C2 or higher, or (ii) at least four of the six ortho positions are C1, and optionally all six of the ortho positions are non-hydrogen.
A metal complex compound comprising:
- a rare earth metal ion;
- and
- a triaryl boron ligand,
- wherein the triarylboron ligand comprises a boron atom bound to three substituted or unsubstituted aryl moieties such that there are six substituent positions on the aryl moieties that are ortho to the boron, and the boron is sterically encumbered by substituents at two or more of the six ortho positions, wherein (i) at least two of the six ortho positions are C2-or-higher or (ii) at least four of the six ortho positions are C1, and optionally all six of the ortho positions are non-hydrogen, and
- wherein at least one of the three aryl moieties comprises a moiety that is capable of binding a rare earth metal ion.
Ligand 4, Ligand 5, Ligand 6, L10, L20, L30, L40, L50, L60, L70, or L80.
1Tb, 1Eu, 2Tb, 2Eu, 3Tb, 4Tb, 5Eu, 6Eu, Tb(L20)3(Lnon-emissive)x, Tb(L30)3(Lnon-emissive)x, Tb(L60)3(Lnon-emissive)x, Eu-10, Eu-20, Eu(L60)3(Lnon-emissive)x, Tb(L60)3(Lnon-emissive)x, Tb(L70)3(Lnon-emissive)x, Tb(L80)3(Lnon-emissive)x, Eu(L20)3(Lnon-emissive)x, Eu(L30)3(Lnon-emissive)x, Eu(L60)3(Lnon-emissive)x, Eu(L60)3(Lnon-emissive)x, Eu(L70)3(Lnon-emissive)x, or Eu(L80)3(Lnon-emissive)x, where x is a number from 1 to 6, and Lnon-emissive is a ligand that does not enhance Ln emission.
A method of making 1Tb, comprising:
- combining dissolved potassium 4-(dimesitylboryl)-2,3,5,6-tetramethylbenzoate and dissolved Tb(NO3)3.6H2O;
- and
- isolating product 1Tb.
A method of making 2Tb, comprising:
- combining dissolved potassium 4′-(dimesitylboryl)biphenyl-4-carboxylate and dissolved Tb(NO3)3.6H2O;
- and
- isolating product 2Tb.
A method of making 1Eu, comprising:
- combining dissolved Eu(NO3)3.6H2O and dissolved 4-(dimesitylboryl)-2,3,5,6-tetramethylbenzoate;
- and
- isolating product 1Eu.
A method of making 2Eu, comprising:
- combining dissolved Eu(NO3)3.6H2O and dissolved potassium 4′-(dimesitylboryl)biphenyl-4-carboxylate;
- and
- isolating product 2Eu.
A method of making 3Tb, comprising:
- combining dissolved Tb(NO3)3.6H2O and dissolved tris(2′,3′,5′,6′-tetramethylbiphenyl-4-carboxylic acid)borane;
- and
- isolating product 3Tb.
A method of making 4Tb, comprising:
- combining dissolved Tb(NO3)3.6H2O and dissolved tris(2,3,5,6-tetramethyl-4-benzoic acid)borane;
- and
- isolating product 4Tb.
A method of making 5Eu, comprising:
- forming a suspension of 5 and 1,10-phenanthroline;
- heating;
- increasing pH;
- mixing the suspension with dissolved Europium(III)-chloride.6H2O;
- and
- isolating 5Eu.
A method of making 6Eu, comprising:
- forming a suspension of 6 and 1,10-phenanthroline;
- heating;
- increasing pH;
- mixing the suspension with dissolved Europium(III)-chloride.6H2O;
- heating to about 60° C.;
- cooling;
- and
- isolating 6Eu.
A method of making Ln-10, Ln-20, Ln(L30)3(Lnon-emissive)x, Ln(L40)3(Lnon-emissive)x, Ln(L50)3(Lnon-emissive)x, Ln(L60)3(Lnon-emissive)x, Ln(L70)3(Lnon-emissive)x, Ln(L80)3(Lnon-emissive)x comprising:
- forming a suspension of Lnon-emissive and boryl ligand L-10, L-20, L30, L40, L50, L60, L70, or L80;
- optionally heating;
- increasing pH;
- mixing the suspension with dissolved Ln(III) salt;
- optionally heating;
- cooling;
- and
- isolating Ln(boryl ligand)3(Lnon-emissive)x,
- where x is a number between 1 and 6 and Lnon-emissive is a ligand that does not enhance Ln emission.
A compound of general formula Ln(Bacac)3(Lnon-emissive)x, where Ln is a rare earth metal ion, Bacac can be the same or different and is a boryl functionalized diketone liand, Lnon-emissive is the same or different and is a non-emissive ligand, and x is a number from 1 to 6.
Dependencies are inferred from the claim text.