A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence
Most of the existing optical methods for CuII detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have be...
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| Published in: | Journal of luminescence Vol. 171; pp. 191 - 197 |
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01-03-2016
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| Abstract | Most of the existing optical methods for CuII detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of CuII ions based on both visible (TbIII, EuIII) and near-infrared (NdIII, YbIII) emission. Quantum yields of the characteristic LnIII emission signals increases by at least two-orders of magnitude upon addition of CuII into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of CuII ions does not significantly affect the energy positions of the singlet (32,260cm−1) and triplet (25,640–25,970cm−1) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce CuII to CuI has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards CuII over other transition metal ions: the addition of divalent ZnII, CdII, PdII, NiII, CoII or trivalent FeIII, GaIII, InIII ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of CuII results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the design of efficient “turn-on” sensors for CuII ions based on visible and near-infrared LnIII luminescence. |
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| AbstractList | Most of the existing optical methods for CuII detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of CuII ions based on both visible (TbIII, EuIII) and near-infrared (NdIII, YbIII) emission. Quantum yields of the characteristic LnIII emission signals increases by at least two-orders of magnitude upon addition of CuII into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of CuII ions does not significantly affect the energy positions of the singlet (32,260 cm−1) and triplet (25,640–25,970 cm−1) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce CuII to CuI has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards CuII over other transition metal ions: the addition of divalent ZnII, CdII, PdII, NiII, CoII or trivalent FeIII, GaIII, InIII ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of CuII results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the design of efficient “turn-on” sensors for CuII ions based on visible and near-infrared LnIII luminescence. Most of the existing optical methods for CuII detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of CuII ions based on both visible (TbIII, EuIII) and near-infrared (NdIII, YbIII) emission. Quantum yields of the characteristic LnIII emission signals increases by at least two-orders of magnitude upon addition of CuII into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of CuII ions does not significantly affect the energy positions of the singlet (32,260cm−1) and triplet (25,640–25,970cm−1) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce CuII to CuI has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards CuII over other transition metal ions: the addition of divalent ZnII, CdII, PdII, NiII, CoII or trivalent FeIII, GaIII, InIII ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of CuII results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the design of efficient “turn-on” sensors for CuII ions based on visible and near-infrared LnIII luminescence. |
| Author | Eliseeva, Svetlana V. Petoud, Stéphane Meshkova, Svetlana B. Liasotskyi, Valerii S. Golovach, Iurii P. Antonovich, Valery P. |
| Author_xml | – sequence: 1 givenname: Svetlana V. surname: Eliseeva fullname: Eliseeva, Svetlana V. email: svetlana.eliseeva@cnrs-orleans.fr organization: Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2, France – sequence: 2 givenname: Iurii P. surname: Golovach fullname: Golovach, Iurii P. organization: I.I.Mechnikov Odessa National University, 2 Dvoryanska street, 65082 Odessa, Ukraine – sequence: 3 givenname: Valerii S. surname: Liasotskyi fullname: Liasotskyi, Valerii S. organization: I.I.Mechnikov Odessa National University, 2 Dvoryanska street, 65082 Odessa, Ukraine – sequence: 4 givenname: Valery P. surname: Antonovich fullname: Antonovich, Valery P. organization: A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa, Ukraine – sequence: 5 givenname: Stéphane surname: Petoud fullname: Petoud, Stéphane email: stephane.petoud@inserm.fr organization: Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2, France – sequence: 6 givenname: Svetlana B. surname: Meshkova fullname: Meshkova, Svetlana B. email: s_meshkova@ukr.net organization: A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa, Ukraine |
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| CitedBy_id | crossref_primary_10_1007_s11431_017_9212_7 crossref_primary_10_1039_C7DT04203E crossref_primary_10_1002_bio_3883 crossref_primary_10_1002_chem_202002282 crossref_primary_10_1002_chem_201700567 crossref_primary_10_1039_C8RA01037D crossref_primary_10_1016_j_molstruc_2019_127160 crossref_primary_10_1134_S1061934820030144 crossref_primary_10_1021_acs_inorgchem_9b02934 |
| Cites_doi | 10.1002/cphc.201200367 10.1002/anie.200463081 10.1134/S106193480805002X 10.1007/s10895-010-0787-x 10.1039/c3ay41365a 10.1002/jlac.198019800311 10.1134/S0036023609070079 10.1063/1.1669895 10.1021/cr980446m 10.1016/j.saa.2011.03.018 10.1021/j100272a015 10.1038/nm0103-123 10.1063/1.1669893 10.1039/b901567a 10.1016/S0010-8545(01)00341-1 10.1007/s10812-005-0125-2 10.1023/B:JANC.0000043910.69823.18 10.1021/ic202322f 10.1021/cr900223a 10.1039/B316176E 10.1021/cr900263j 10.1021/j150657a006 10.1021/j100800a010 10.1021/ac60087a052 10.1016/j.jorganchem.2010.10.023 10.1007/s00706-009-0135-5 10.1016/j.tetlet.2010.07.174 10.1016/j.poly.2011.05.008 10.1063/1.1669894 10.1016/j.aca.2011.09.034 10.1007/s10895-012-1098-1 10.1021/cr900134a 10.1021/jp4008015 10.1063/1.1669896 |
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| Keywords | Visible Lanthanide Copper Luminescence Near-infrared |
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| Snippet | Most of the existing optical methods for CuII detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an... |
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| SubjectTerms | Copper Lanthanide Life Sciences Luminescence Near-infrared Visible |
| Title | A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence |
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