Reversible Luminescence Switching of a Redox-Active Ferrocene–Europium Dyad

Tropiano, Manuel; Kilah, N. L.; Morten, Michael J.; Rahman, Habibur; Davis, Jason J.; Beer, Paul D.; Faulkner, Stephen

doi:10.1021/ja203069s

Cited by 153 publications

(129 citation statements)

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“…The spectral overlap between the absorption and emission bands promotes a decrease of the emission quantum yield with an increase of the nonradiative rate constant, k nr . 25 Filter effects due to the spectral overlap also decrease the emission quantum yield. Thus, luminescence-switchable lanthanide compounds without this spectral overlap are expected to open up new strategies for molecular materials science and engineering. Here, we focus on luminescence-switchable lanthanide compounds that have dynamic molecular motion without a color-changeable absorption band in the visible region.…”

Section: ■ Introductionmentioning

confidence: 99%

Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units

et al. 2015

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Enhanced luminescence of a lanthanide complex with dynamic polarization of the excited state and molecular motion is introduced. The luminescent lanthanide complex is composed of one Eu(hfa)3 (hfa, hexafluoroacetylacetonate) and two phosphine oxide ligands with ruthenocenyl units Rc, [Eu(hfa)3(RcPO)2] (RcPO = diphenylphosphorylruthenocene). The ruthenocenyl units in the phosphine oxide ligands play an important role of switching for dynamic molecular polarization and motion in liquid media. The oxidation states of the ruthenocenyl unit (Rc(1+)/Rc(1+)) are controlled by potentiostatic polarization. Eu(III) complexes attached with bidentate phosphine oxide ligands containing ruthenocenyl units, [Eu(hfa)3(RcBPO)] (RcBPO = 1,1'-bis(diphenylphosphoryl)ruthenocene), and with bidentate phosphine oxide ligands, [Eu(hfa)3(BIPHEPO)] (BIPHEPO =1,1'-biphenyl-2,2'-diylbis(diphenylphosphine oxide), were also prepared as references. The coordination structures and electrochemical properties were analyzed using single crystal X-ray analysis, cyclic voltammetry, and absorption spectroscopy measurements. The luminescence properties were estimated using an optoelectrochemical cell. Under potentiostatic polarization, a significant enhancement of luminescence was successfully observed for [Eu(hfa)3(RcPO)2], while no spectral change was observed for [Eu(hfa)3(RcBPO)]. In this study, the remarkable enhanced luminescence phenomena of Eu(III) complex based on the dynamic molecular motion under potentiostatic polarization have been performed.

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Section: ■ Introductionmentioning

confidence: 99%

Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units

et al. 2015

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“…Starting with the absorption of light by the ligands, energy is subsequently transferred to the metal ion, the antenna effect, followed by the characteristic emission of the lanthanide ion678910. Luminescent europium complexes, in particular, act as light conversion molecular devices by absorbing ultraviolet (UV) light and by emitting light in the red visible spectral region.…”

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confidence: 99%

A Comprehensive Strategy to Boost the Quantum Yield of Luminescence of Europium Complexes

Lima

Gonçalves

Júnior

et al. 2013

Sci Rep

118

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Lanthanide luminescence has many important applications in anion sensing, protein recognition, nanosized phosphorescent devices, optoelectronic devices, immunoassays, etc. Luminescent europium complexes, in particular, act as light conversion molecular devices by absorbing ultraviolet (UV) light and by emitting light in the red visible spectral region. The quantum yield of luminescence is defined as the ratio of the number of photons emitted over the number of UV photons absorbed. The higher the quantum yield of luminescence, the higher the sensitivity of the application. Here we advance a conjecture that allows the design of europium complexes with higher values of quantum yields by simply increasing the diversity of good ligands coordinated to the lanthanide ion. Indeed, for the studied cases, the percent boost obtained on the quantum yield proved to be strong: of up to 81%, accompanied by faster radiative rate constants, since the emission becomes less forbidden.

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“…Indeed, the spectral overlap between the europium donor and ferrocenium acceptor is such that effective Förster energy transfer takes place only when the ferrocene unit is oxidised and does not affect the luminesce of the assembly when in its reduced state. This is the first example of electrochemical tuning of lanthanide luminescence and opens up new opportunities for signal manipulation and responsive imaging [60]. The sevencoordinate lanthanide complex with an appended carboxylate-containing arm ( Fig.…”

Section: Responsive Multimetallic Systemsmentioning

confidence: 96%

“…For instance, we have employed click chemistry methods to link propargyl DO3A complexes together ( Fig. 9.15) to form homobinuclear lanthanide complexes [59], and extended this approach to the preparation of d-f hybrids containing redox active ferrocene chromophores [60]. f-f´heterometallic systems can also be produced by linking stable components together, for instance in the preparation of tetranuclear .…”

Section: Heterometallic Complexes Derived From Bridging and Multi-commentioning

confidence: 99%

Heterometallic Complexes Containing Lanthanides

Faulkner

Tropiano

2014

Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials

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The synthesis of tetranuclear gold complexes, as tructurally unprecedented octanuclear complex with ap lanar [Au I 8 ]c ore,a nd pentanuclear [Au I 4 M I ](M = Cu, Ag) complexes is presented. The linear [Au I 4 ]complex undergoes C À Hf unctionalization of carbonyl compounds under mild reaction conditions.I na ddition, [Au I 4 Ag I ]c atalyzes the carbonylation of primary amines to form ureas under homogeneous conditions with efficiencies higher than those achieved by gold nanoparticles. Following the pioneering work of the groups of Hutchings [1] and Haruta [2] on the oxidation of hydrocarbons and CO,many gold clusters and nanoparticles have been structurally characterized and studied in catalysis. [3,4] Recently,s mall gold clusters have been found to activate the CÀIb ond of iodobenzene in the gas phase [5] and to catalyze reactions usually performed by mononuclear gold complexes. [6] However ,t he actual structures of these clusters have not been determined. In this context, it is important to note that the group of Bertrand reported the synthesis of mixed-valence trinuclear [Au 0 2 Au I ]c lusters which are catalysts for the carbonylation of aliphatic amines under homogeneous conditions. [7] As part of our program on the study of the catalytic activity of well-defined gold(I) clusters, [8] we now report ar eady synthesis of linear [Au 4 ], pentagonal [Au I 4 M I ](M= Cu, Ag), and octagonal [Au 8 ]c omplexes.T he linear [Au 4 ] complex reacts with carbonyl compounds by CÀHf unction-alization to form square-planar complexes.F urthermore,t he pentanuclear complex [Au I 4 Ag I ]h as been found to be an excellent homogeneous catalyst for the carbonylation of amines. Our synthesis started from the dinuclear gold(I) complex 1,w hich is quantitatively prepared by mixing 2,6-bis(diphe-Scheme 1. Synthesis of the [Au 4 ]c omplexes 2 and 3 and the [Au 8 ] complex 4.A= SbF 6 ,B= BF 4 .

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Reversible Luminescence Switching of a Redox-Active Ferrocene–Europium Dyad

Abstract: The copper-catalyzed cycloaddition reaction between a propargyl-appended europium complex and azidomethylferrocene yields a d-f dyad whose photophysical properties can be reversibly switched by varying the oxidation state of the ferrocene chromophore.

Cited by 153 publications

References 31 publications

Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units

Enhanced Electric Dipole Transition in Lanthanide Complex with Organometallic Ruthenocene Units

A Comprehensive Strategy to Boost the Quantum Yield of Luminescence of Europium Complexes

Heterometallic Complexes Containing Lanthanides

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