Sensitised near infrared emission from lanthanides via anion-templated assembly of d–f heteronuclear [2]pseudorotaxanes

Sambrook, Mark R.; Curiel, David; Hayes, Elizabeth J.; Beer, Paul D.; Pope, Simon J. A.; Faulkner, Stephen

doi:10.1039/b601017b

Cited by 57 publications

(33 citation statements)

References 23 publications

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“…For instance, Sambrook et al prepared a pseudo-rotaxane (18) templated around a chloride ion (Fig. 9) in which lanthanide ions are bound to the "thread" while a luminescent rhenium complex is bound to the macrocycle component [49]. Thus there is no direct link between the donor chromophore and the lanthanide ion, and Dexter exchange is not viable in the absence of bonds enforcing Förster energy transfer.…”

Section: Assembly Of Arrays From Stable Building Blocksmentioning

confidence: 98%

Lanthanide Assemblies and Polymetallic Complexes

Faulkner

Sykes

2010

Lanthanide Luminescence

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Section: Assembly Of Arrays From Stable Building Blocksmentioning

confidence: 98%

Lanthanide Assemblies and Polymetallic Complexes

Faulkner

Sykes

2010

Lanthanide Luminescence

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“…42 It was demonstrated initially that by using a thread which contained either no lanthanide cation, or a gadolinium cation that was unable to undergo energy transfer with the Re(I)-bipyridyl center, an enhancement of the Re-bipyridyl-MLCT band was observed upon pseudorotaxane formation. However, addition of neodymium thread 12 resulted in a significant reduction in the MLCT emission, with the concomitant appearance of a near-IR lanthanide emission band due to energy transfer between the MLCT excited state and the lanthanide complex.…”

Section: ■ Exploiting the Dynamics Of Interlocked Host Systems For Anmentioning

confidence: 99%

Rotaxane and Catenane Host Structures for Sensing Charged Guest Species

2014

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CONSPECTUS: The promise of mechanically interlocked architectures, such as rotaxanes and catenanes, as prototypical molecular switches and shuttles for nanotechnological applications, has stimulated an ever increasing interest in their synthesis and function. The elaborate host cavities of interlocked structures, however, can also offer a novel approach toward molecular recognition: this Account describes the use of rotaxane and catenane host systems for binding charged guest species, and for providing sensing capability through an integrated optical or electrochemical reporter group. Particular attention is drawn to the exploitation of the unusual dynamic properties of interlocked molecules, such as guest-induced shuttling or conformational switching, as a sophisticated means of achieving a selective and functional sensor response. We initially survey interlocked host systems capable of sensing cationic guests, before focusing on our accomplishments in synthesizing rotaxanes and catenanes designed for the more challenging task of selective anion sensing. In our group, we have developed the use of discrete anionic templation to prepare mechanically interlocked structures for anion recognition applications. Removal of the anion template reveals an interlocked host system, possessing a unique three-dimensional geometrically restrained binding cavity formed between the interlocked components, which exhibits impressive selectivity toward complementary anionic guest species. By incorporating reporter groups within such systems, we have developed both electrochemical and optical anion sensors which can achieve highly selective sensing of anionic guests. Transition metals, lanthanides, and organic fluorophores integrated within the mechanically bonded structural framework of the receptor are perturbed by the binding of the guest, with a concomitant change in the emission profile. We have also exploited the unique dynamics of interlocked hosts by demonstrating that an anion-induced conformational change can be used as a means of signal transduction. Electrochemical sensing has been realized by integration of the redox-active ferrocene functionality within a range of rotaxane and catenanes; binding of an anion perturbs the metallocene, leading to a cathodic shift in the ferrocene/ferrocenium redox couple. In order to obtain practical sensors for target charged guest species, confinement of receptors at a surface is necessary in order to develop robust, reuseable devices. Surface confinement also offers advantages over solution based receptors, including amplification of signal, enhanced guest binding thermodynamics and the negation of solubility problems. We have fabricated anion-templated rotaxanes and catenanes on gold electrode surfaces and demonstrated that the resulting mechanically bonded self-assembled monolayers are electrochemically responsive to the binding of anions, a crucial first step toward the advancement of sophisticated, highly selective, anion sensory devices. Rotaxane and catenane host molecules may be...

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“…[ [4] and their line-like emission bands resulti n high colourp urity of the emitted light. [6,7] Hence, trivalent lanthanide ion complexes are an attractive choice for the sensing of OP CWAs if the target OP CWAs can modulate the intense metal-centred emission. [5] Ap articular issue for lanthanide complexes is efficient non-radiative deactivation of their excited states by OH oscillators, such as water.…”

Section: Sensing Considerationsmentioning

confidence: 99%

Mechanistic Insights into the Luminescent Sensing of Organophosphorus Chemical Warfare Agents and Simulants Using Trivalent Lanthanide Complexes

Dennison

Johnston

2015

Chemistry A European J

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Organophosphorus chemical warfare agents (OP CWAs) are potent acetylcholinesterase inhibitors that can cause incapacitation and death within minutes of exposure, and furthermore are largely undetectable by the human senses. Fast, efficient, sensitive and selective detection of these compounds is therefore critical to minimise exposure. Traditional molecular-based sensing approaches have exploited the chemical reactivity of the OP CWAs, whereas more recently supramolecular-based approaches using non-covalent interactions have gained momentum. This is due, in part, to the potential development of sensors with second-generation properties, such as reversibility and multifunction capabilities. Supramolecular sensors also offer opportunities for incorporation of metal ions allowing for the exploitation of their unique properties. In particular, trivalent lanthanide ions are being increasingly used in the OP CWA sensing event and their use in supramolecular sensors is discussed in this Minireview. We focus on the fundamental interactions of simple lanthanide systems with OP CWAs and simulants, along with the development of more elaborate and complex systems including those containing nanotubes, polymers and gold nanoparticles. Whilst literature investigations into lanthanide-based OP CWA detection systems are relatively scarce, their unique and versatile properties provide a promising platform for the development of more efficient and complex sensing systems into the future.

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Sensitised near infrared emission from lanthanides via anion-templated assembly of d–f heteronuclear [2]pseudorotaxanes

Cited by 57 publications

References 23 publications

Lanthanide Assemblies and Polymetallic Complexes

Lanthanide Assemblies and Polymetallic Complexes

Rotaxane and Catenane Host Structures for Sensing Charged Guest Species

Mechanistic Insights into the Luminescent Sensing of Organophosphorus Chemical Warfare Agents and Simulants Using Trivalent Lanthanide Complexes

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