Circularly polarized luminescence and energy transfer studies on carboxylic acid complexes of europium(III) and terbium(III) in solution

Luk, Chun Ka; Richardson, F. S.

doi:10.1021/ja00856a012

Cited by 68 publications

(29 citation statements)

References 11 publications

(18 reference statements)

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“…In such complexes the presence of dissymmetry in the ligand field means that the electric and magnetic dipole moments associated with the transitions are nonorthogonal and therefore optical activity can be observed. 62 This is in accordance with equation 8, defined in Section 1.2.2.…”

Section: Understanding the Origin Of Chirality In Lanthanide Complexessupporting

confidence: 85%

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

2012

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source• a link is made to the metadata record in Durham E-Theses• the full-text is not changed in any wayThe full-text must not be sold in any format or medium without the formal permission of the copyright holders. Statement of CopyrightThe copyright of this thesis rests with the author. No quotations should be published without prior consent and information derived from it must be acknowledged. ABSTRACT -ii - ABSTRACTA series of studies has been undertaken to facilitate the identification and development of chiral lanthanide complexes that are able to report on changes in their local environment through modulation of the circular polarization of their emission. Reports of such systems remain relatively rare in the literature, notwithstanding the prevalence and importance of chirality in biological systems.The work described herein is separated into five chapters, the first of which comprises a discussion of relevant background information, along with a comprehensive review of responsive lanthanide-based CPL probes reported to date. A classification of these probes is built up, which informs the content of the following three chapters.Chapter 2 describes work undertaken in the pursuit of a novel lanthanide-based system for use as a CPL probe for the detection of proteins. The synthesis of an enantiopure lanthanide complex was undertaken and characterisation of this system carried out with reference to a structurally related racemic complex. A series of comparative investigations designed to probe the relative protein binding capability of these complexes was subsequently performed, which revealed that the observation of induced CPL from racemic lanthanide systems may be brought about by a change in complex constitution. This is the first example of such an effect from a well-defined racemic lanthanide complex in solution. Chapter 3 goes on to detail studies undertaken to demonstrate the utility of this racemic lanthanide system as a probe for chiral detection.Chapter 4 describes investigations carried out in an attempt to identify new systems exhibiting chiral quenching effects in solution. Initially, two pairs of enantiomeric electron-rich quenching species were assessed for their ability to quench the emission from an enantiopure DOTA-derived lanthanide complex differentially. Subsequently, investigations were focussed on examining the quenching of emission from novel enantiopure lanthanide complexes based on a 1,4,7-triazacyclononane framework, using cobalt complexes as the quenching species.Finally, Chapter 5 contains experimental procedures for each compound synthesised, as well as general experimental procedures.

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Section: Understanding the Origin Of Chirality In Lanthanide Complexessupporting

confidence: 85%

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

2012

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“…This is the reason for which CPL spectroscopy has been mainly applied to lanthanide(III) complexes, where large g lum values can be reached for the magnetically-allowed intraconfigurational f – f transitions of the lanthanide ion. 17 Unfortunately, the paradox of this requirement is that g lum may be quite large (currently up to 1.38) for such selected transitions, 14,18 but they have usually very low intensity, and therefore are more difficult to measure. It is worth noting that the same arguments apply to CD spectroscopy, where it is often easier to study the n→π* transitions of chiral ketones than π→π* transitions.…”

Section: Cpl Measurementmentioning

confidence: 99%

“…This phenomenon originates from the passing of linearly polarized light through the very slightly birefringent PEM. 2b,14,17–19 Since the intensity of a linear polarization signal is much larger than of a true CPL signal, it may lead to signals of comparable magnitudes, even if the birefringence is usually small (< 5%). As an example, luminescence that is 10% linearly polarized may be converted by this effect to circular polarization of about 0.5%, which is often larger than the true CPL signal.…”

Section: Cpl Measurementmentioning

confidence: 99%

Circularly Polarized Luminescence from Simple Organic Molecules

Sánchez‐Carnerero

Agarrabeitia

Moreno

et al. 2015

Chemistry A European J

858

578

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This article aims to show the identity of “CPL-active simple organic molecules” as a new concept in Organic Chemistry due to the potential interest of these molecules, as availed by the exponentially growing number of research articles related to them. In particular, it describes and highlights the interest and difficulty in developing chiral simple (small and nonaggregated) organic molecules able to emit left- or right-circularly polarized light efficiently, the efforts realized up to now to reach this challenging objective, and the most significant milestones achieved to date. General guidelines for the preparation of these interesting molecules are also presented.

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“…In addition, information concerning metal-ion environments and the associated chiral structures of metal-containing biological systems could be obtained through the measurement of CPL. The considerable increase in the use of CPL spectroscopy most probably originated from the discovery, of Luk and Richardson in 1975, that luminescence from intraconfigurational f ↔ f transitions of the lanthanide(III) ions obeying magnetic-dipole selection rules often showed large circular polarization 2. Transitions that satisfy the formal selection rules of Δ J = 0, ± 1 (except 0 ↔ 0) are magnetic-dipole allowed, where J stands for the total angular momentum quantum number found in the definition of the term symbol, 2 S +1 L J , describing the electronic states of lanthanides 3.…”

Section: Introductionmentioning

confidence: 99%

A Promising Change in the Selection of the Circular Polarization Excitation Used in the Measurement of Eu(III) Circularly Polarized Luminescence

Muller

2008

J. Phys. Chem. A

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A judicious change in the selected transition used for circular polarization excitation will overcome the low oscillator strength limitation of the currently allowed magnetic-dipole 5 D 1 ← 7 F 2 (Eu(III)) transition chosen for circularly polarized luminescence (CPL) measurement. The proposed allowed magnetic-dipole 5 D 1 ← 7 F 0 (Eu(III)) transition will facilitate the detection of CPL from the Eu(III) systems of interest. CPL on the acetonitrile solution of the chiral tris complex of Eu(III) with (R,R)-, recently suggested as an effective and reliable CPL calibrating agent, confirms the feasibility of the proposed experimental procedure. A comparable CPL activity exhibited by the acetonitrile solution of [Eu((R,R)-1) 3 ] 3+ following direct excitation in the spectral range of the 5 D 1 ← 7 F 0 transition and upon indirect excitation through the ligand absorption bands (λ exc = 308 nm) was observed. This confirms that the recommended magnetic-dipole allowed absorption transition, 5 D 1 ← 7 F 0 , is the transition to be considered in the measurement of CPL. This work provides critical direction for the continued instrumental improvements that can be done for developing CPL into a biomolecular structural probe.

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Circularly polarized luminescence and energy transfer studies on carboxylic acid complexes of europium(III) and terbium(III) in solution

Cited by 68 publications

References 11 publications

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

Circularly Polarized Luminescence from Simple Organic Molecules

A Promising Change in the Selection of the Circular Polarization Excitation Used in the Measurement of Eu(III) Circularly Polarized Luminescence

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