Switch-on luminescence detection of steroids by tris(bipyridyl)ruthenium(ii) complexes containing multiple cyclodextrin binding sites

Nelissen, Hubertus F. M.; Schut, Arnoldus F. J.; Venema, Fokke; Feiters, Martinus C.; Nolte, Roeland J. M.

doi:10.1039/b000271m

Cited by 54 publications

(30 citation statements)

References 8 publications

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“…[10,12] This ligand was used to construct the two ruthenium(ii) complexes 1 and 2. [15] Compound 2 was synthesised by treating three equivalents of 3 with RuCl 3 in mixture of ethanol/water (1:1 v/v) heated under reflux.…”

Section: Resultsmentioning

confidence: 99%

“…The resulting high quantum yield and emission lifetime, in particular of complex 2, make this compound very interesting for use in sensor devices, as we have already briefly communicated. [12] Through a comparison of the time resolved luminescence studies of viologen 4 and 6, together with the determination of the binding constants for these compounds to the complexes 1 and 2 via calorimetric titration, we have established that cooperative effects of two b-cyclodextrins in the binding of the viologen guests are present. NMR spectroscopy has provided valuable insights into the conformational behaviour of compounds 1 and 2 in aqueous solutions.…”

Section: Resultsmentioning

confidence: 99%

“…[12,13] In this paper we report the synthesis of two tris(bipyridine)ruthenium(ii) complexes bearing two (1), and six (2) bcyclodextrin (CD) moieties from the bipyridine-spaced dimer 3, as shown in Scheme 1. The cyclodextrins are connected to the 4,4'-position of the bipyridine ligand to avoid problems with steric crowding around the metal centre.…”

Section: Introductionmentioning

confidence: 99%

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Photoinduced Electron Transfer between Metal-Coordinated Cyclodextrin Assemblies and Viologens

Nelissen¹,

Kercher

Cola

et al. 2002

Chem. Eur. J.

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Two novel tris(bipyridine)ruthenium(ii) complexes bearing two and six b-cyclodextrin binding sites on their ligands have been synthesised and characterised. Complex 1, bearing two cyclodextrins, adopts a conformation in aqueous solution where parts of the aromatic ligands are self-included into the cyclodextrin moieties. This results in a loss of symmetry of the complex and gives rise to a much more complicated 1 H NMR spectrum than expected. Photophysical studies indicate that the appended cyclodextrins protect the luminescent ruthenium core from quenching by oxygen, which results in longer excited state lifetimes and higher emission quantum yields compared with the reference compound, the unsubstituted ruthenium tris(bipyridine). Inclusion of suitable guests such as dialkyl-viologens leads to a quenching of the luminescence of the central unit. In these supramolecular donor ± acceptor dyads an efficient pho-toinduced electron transfer from the excited ruthenium moiety (the donor) to the viologen unit (the acceptor) is observed. The alkyl chain length of the acceptor plays an important role on the binding properties; when it exceeds a certain limit the binding becomes strong enough for electron transfer to occur. Interestingly, a viologen with only one long alkyl tail instead of two shows no efficient quenching; this indicates that cooperative interactions between two cyclodextrins binding one viologen are essential to raise the binding constant of the supramolecular dyad.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photoinduced Electron Transfer between Metal-Coordinated Cyclodextrin Assemblies and Viologens

Nelissen¹,

Kercher

Cola

et al. 2002

Chem. Eur. J.

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“…Self-assembled systems between ruthenium-bipyridine centers and various electron or energy acceptors have recently attracted much interest. [8][9][10] We are interested in studying photoinduced processes between metal units assembled in water through noncovalent interactions. We have previously introduced photoactive metals onto cyclodextrin rims for the assembly of photoactive units brought together by the cyclodextrin cavity.…”

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Vectorial Control of Energy‐Transfer Processes in Metallocyclodextrin Heterometallic Assemblies

et al. 2003

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In recent years, the importance of miniature photomolecular devices in nanoscale technology has led to the design of polymetallic supramolecular assemblies. [1][2][3] The employment of polyelectronic metal centers in a single supramolecular structure provides the basis for the development of molecular energy-conversion systems and wires in macromolecular systems. [4][5][6][7] Multistep reactions are usually required to link metallic building blocks together by means of covalent bonds; such multistep processes result in poor yields and synthetic complexity. Noncovalently assembled systems, in contrast, may allow control of the photoinduced processes by a simple choice of the assembled photoactive components. The noncovalent assembly of units in water presents other opportunities, not only to mimic natural processes, but also to provide easily accessible architectures. Self-assembled systems between ruthenium-bipyridine centers and various electron or energy acceptors have recently attracted much interest. [8][9][10] We are interested in studying photoinduced processes between metal units assembled in water through noncovalent interactions. We have previously introduced photoactive metals onto cyclodextrin rims for the assembly of photoactive units brought together by the cyclodextrin cavity. [11][12][13][14] Herein, we present a ruthenium tris(bipyridyl) cyclodextrin "wheel", [Ru(b-CD-mbpy) 3 ] 2+ (1; b-CD-mbpy = 6-mono[4-methyl(4'-dimethyl-2,2'-bipyridyl] permethylated b-cyclodextrin which was isolated as the PF 6 salt 1-(PF 6 ) 2 and which could be converted into the Cl salt 1-Cl 2 to enhance its solubility) that acts as both energy donor and acceptor leading to a versatile system for communication between the inner metal core and the outer guest unit by energy transfer; metal-complex guests based on osmium(ii) and iridium(iii) terpyridine species with biphenyl or adamantyl tails attached to one of the ligands have been employed to examine the importance of the included tail in the photoinduced process (Figure 1).Compound 1, is an attractive luminescent receptor molecule with three cyclodextrin cups available for recognition. Solutions of 1 in water with 10 % acetonitrile exhibit luminescence at room temperature at 622 nm (F = 0.027, t aerated = 460 ns, t degassed = 640 ns) upon excitation at the metalto-ligand charge transfer (MLCT) band at 436 nm. Comparison of the photophysical properties of this complex with the parent complex [Ru(mbpy) 3 ][PF 6 ] 2 , (mbpy = 4,4'-dimethyl-2,2'-bipyridine) which bears no cyclodextrins, indicates that cyclodextrin substitution does not have a significant effect.Osmium(ii)-based guests, have been employed to play the role of energy acceptors whereas iridium(iii)-based guests were used as energy donors for the Ru II center. The guests have hydrophobic biphenyl and adamantyl tails to ensure high binding constants in the cyclodextrin cavity. The nature of the hydrophobic tail, aliphatic versus aromatic, is selected to examine its effect in the photoinduced processes. Considerin...

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“…In contrast, there are several papers which describe the fluorescent binding property of CyD derivatives substituted at the lower rim (C-2 or C-3 positions) and the difficulties to sulfonate the secondary hydroxyl group. [13][14][15][16][17] However, Teranishi has prepared mono-and regioselectively di-sulfonyl β-and γ-CyDs at the lower rim (C-2 position) from sulfonyl imidazole treated with molecular sieves 4A under mild condition. [18][19][20][21] These new modifications produced CyDs at the lower rim which are very interesting.…”

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Selective Fluorescent Molecular Sensing Based on 2A,2D-Disulfonyl Dibenzosulfolane-diphenyl-capped β-Cyclodextrin for Phenolic Guests

et al. 2002

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Cyclodextrins (CyDs), which are torus-shaped cyclic oligomers composed of D-glucopyranose, are named α-, β-and γ-for the hexamer, heptamer and octamer, respectively. CyDs form inclusion complexes with various organic guests in an aqueous solution. 1 Recently, chromophore-modified CyDs have been shown to exhibit remarkable variations in circular dichroism, absorption and fluorescence spectra, depending on the formation of host-guest complexation; 2-6 therefore, the appended chromophores can be used as a probe to sense guest molecules. Previously, we have discussed fluorescence molecular sensing systems of CyDs modified with fluorescent active units at the upper rim. [7][8][9][10][11][12] In these systems, it was found that the fluorescence spectra are most sensitively observed in spectrophotometry, in which variations of guest-induced fluorescence intensities effectively work as a sensing probe, showing much more complete and accurate sensing patterns. In contrast, there are several papers which describe the fluorescent binding property of CyD derivatives substituted at the lower rim (C-2 or C-3 positions) and the difficulties to sulfonate the secondary hydroxyl group. [13][14][15][16][17] However, Teranishi has prepared mono-and regioselectively di-sulfonyl β-and γ-CyDs at the lower rim (C-2 position) from sulfonyl imidazole treated with molecular sieves 4A under mild condition. [18][19][20][21] These new modifications produced CyDs at the lower rim which are very interesting. During the last year, we discussed a selective fluorescent sensing system of CyDs modified with pyrene and tosyl at the lower and upper rims, respectively, 22 in which the pyrene moiety at the lower rim of CyD worked as a more sensitive fluorescent probe to distinguish the structures of steroidal compounds. For a further extension of our work, we tried to study the fluorescent molecular sensing abilities for endocrine disruptors based on β-CyD capping at the lower rim, which is 2 A ,2 D -disulfonyl dibenzosulfolane-diphenyl capped β-CyD (β-1), 23 in an aqueous solution. A couple of fluorescent capped CyDs at the upper rim have been reported that shows a low molecular sensing ability due to a difficulty to move these fluorescent linker. 3,24 However, the host β-1, which is the first example of a regioselectively capped CyD at the lower rim, can peculiarly recognize phenolic guests, such as p-nonylphenol and bisphenol A. Experimental MeasurementsFluorescence spectra were measured at 25˚C using a PerkinElmer LS 40B fluorescence spectrometer. The excitation wavelength was 330 nm, and the excitation and emission slits were 4 nm. Five microliters of guest species (0.5, 0.05 and 0.005 M) in MeOH or dimethyl sulfoxide (DMSO) were injected into a 10 vol.% ethylene glycol aqueous solution of β-1 (2.5 mL, 1.0 × 10 -6 M). This procedure gave a guest concentration of 1.0, 0.1 and 0.01, respectively, in the sample solution. Energy-minimized structuresEnergy-minimized structures were calculated by molecular mechanics using MM2 in CS Chem 3D. The paramete...

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Switch-on luminescence detection of steroids by tris(bipyridyl)ruthenium(ii) complexes containing multiple cyclodextrin binding sites

Abstract: A luminescent ruthenium(II) complex with six cyclodextrin binding sites is shown to switch off its emission upon binding of N,NA-dinonyl-4,4A-bipyridinium bromide and to recover luminescence upon displacement of the bipyridinium ion by a steroid.

Cited by 54 publications

References 8 publications

Photoinduced Electron Transfer between Metal-Coordinated Cyclodextrin Assemblies and Viologens

Photoinduced Electron Transfer between Metal-Coordinated Cyclodextrin Assemblies and Viologens

Vectorial Control of Energy‐Transfer Processes in Metallocyclodextrin Heterometallic Assemblies

Selective Fluorescent Molecular Sensing Based on 2A,2D-Disulfonyl Dibenzosulfolane-diphenyl-capped β-Cyclodextrin for Phenolic Guests

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