Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Circularly polarized luminescence of curium: a new characterization of the 5f actinide complexes.

ABSTRACT: A key distinction between the lanthanide (4f) and the actinide (5f) transition elements is the increased role of f-orbital covalent bonding in the latter. Circularly polarized luminescence (CPL) is an uncommon but powerful spectroscopy which probes the electronic structure of chiral, luminescent complexes or molecules. While there are many examples of CPL spectra for the lanthanides, this report is the first for an actinide. Two chiral, octadentate chelating ligands based on orthoamide phenol (IAM) were used to complex curium(III). While the radioactivity kept the amount of material limited to micromole amounts, spectra of the highly luminescent complexes showed significant emission peak shifts between the different complexes, consistent with ligand field effects previously observed in luminescence spectra.

SUBMITTER: Law GL

PROVIDER: S-EPMC3477521 | biostudies-literature | 2012 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Circularly polarized luminescence of curium: a new characterization of the 5f actinide complexes.

Law Ga-Lai GL Andolina Christopher M CM Xu Jide J Luu Vinh V Rutkowski Philip X PX Muller Gilles G Shuh David K DK Gibson John K JK Raymond Kenneth N KN

Journal of the American Chemical Society 20120911 37

A key distinction between the lanthanide (4f) and the actinide (5f) transition elements is the increased role of f-orbital covalent bonding in the latter. Circularly polarized luminescence (CPL) is an uncommon but powerful spectroscopy which probes the electronic structure of chiral, luminescent complexes or molecules. While there are many examples of CPL spectra for the lanthanides, this report is the first for an actinide. Two chiral, octadentate chelating ligands based on orthoamide phenol (I ...[more]

PMID: 22920726

Similar Datasets

Potential switchable circularly polarized luminescence from chiral cyclometalated platinum(II) complexes.

Project description:A series of chiral cyclometalated platinum(II) complexes, [Pt((-)-L1)(Dmpi)]Cl ((-)-1), [Pt((+)-L1)(Dmpi)]Cl ((+)-1), [Pt((-)-L2)(Dmpi)]Cl ((-)-2), [Pt((+)-L2)(Dmpi)]Cl ((+)-2), [Pt3((-)-L2)2(Dmpi)4](ClO4)4 ((-)-3), and [Pt3((+)-L2)2(Dmpi)4](ClO4)4 ((+)-3) [(-)-L1 = (-)-4,5-pinene-6'-phenyl-2,2'-bipyridine, (+)-L1 = (+)-4,5-pinene-6'-phenyl-2,2'-bipyridine), (-)-L2 = (-)-1,3-bis(2-(4,5-pinene)pyridyl)benzene, (+)-L2 = (+)-1,3-bis(2-(4,5-pinene)pyridyl)benzene, Dmpi = 2,6-dimethylphenyl isocyanide], have been designed and synthesized. In aqueous solutions, (-)-1 and (+)-1 aggregate into one-dimensional helical chain structures through Pt···Pt, ?-?, and hydrophobic-hydrophobic interactions. (-)-3 and (+)-3 represent a novel helical structure with Pt-Pt bonds. The formation of helical structures results in enhanced and distinct chiroptical properties as evidenced by circular dichroism spectra. Circularly polarized luminescence (CPL) was observed from the aggregates of (-)-1 and (+)-1 in water, as well as (-)-3 and (+)-3 in dichloromethane. The CPL activity can be switched reversibly (for (-)-1 and (+)-1) or irreversibly (for (-)-3 and (+)-3) by varying the temperature.

| S-EPMC4286175 | biostudies-literature

Brilliant Sm, Eu, Tb, and Dy chiral lanthanide complexes with strong circularly polarized luminescence.

Project description:The synthesis, characterization, and luminescent behavior of trivalent Sm, Eu, Dy, and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, g(lum), recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments.

| S-EPMC2647558 | biostudies-literature

A [2]Rotaxane-Based Circularly Polarized Luminescence Switch.

Project description:A rotaxane-based molecular shuttle has been synthesized in which the switching of the position of a fluorescent macrocycle on the thread turns "on" or "off" the circularly polarized luminescence (CPL) of the system while maintaining similar fluorescence profiles and quantum yields in both states. The chiroptical activity relies on the chiral information transfer from an ammonium salt incorporating d- or l-phenylalanine residues as chiral stereogenic covalent units to an otherwise achiral crown ether macrocycle bearing a luminescent 2,2'-bipyrene unit when they interact through hydrogen bonding. Each enantiomeric thread induces CPL responses of opposite signs on the macrocycle. Upon addition of base, the switching of the position of the macrocycle to a triazolium group disables the chiral information transfer to the macrocycle, switching "off" the CPL response. The in situ switching upon several acid/base cycles is also demonstrated.

| S-EPMC6975276 | biostudies-literature

Circularly polarized luminescence from organic micro-/nano-structures.

Project description:Circularly polarized light exhibits promising applications in future displays and photonic technologies. Circularly polarized luminescence (CPL) from chiral luminophores is an ideal approach to directly generating circularly polarized light, in which the energy loss induced by the circularly polarized filters can be reduced. Among various chiral luminophores, organic micro-/nano-structures have attracted increasing attention owing to the high quantum efficiency and luminescence dissymmetry factor. Herein, the recent progress of CPL from organic micro-/nano-structures is summarized. Firstly, the design principles of CPL-active organic micro-/nano-structures are expounded from the construction of micro-/nano-structure and the introduction of chirality. Based on these design principles, several typical organic micro-/nano-structures with CPL activity are introduced in detail, including self-assembly of small molecules, self-assembly of π-conjugated polymers, and self-assembly on micro-/nanoscale architectures. Subsequently, we discuss the external stimuli that can regulate CPL performance, including solvents, pH value, metal ions, mechanical force, and temperature. We also summarize the applications of CPL-active materials in organic light-emitting diodes, optical information processing, and chemical and biological sensing. Finally, the current challenges and prospects in this emerging field are presented. It is expected that this review will provide a guide for the design of excellent CPL-active materials.

| S-EPMC8039044 | biostudies-literature

Effect of the Counterion on Circularly Polarized Luminescence of Europium(III) and Samarium(III) Complexes.

Project description:Each enantiopure europium(III) and samarium(III) nitrate and triflate complex of the ligand L, with L = N,N'-bis(2-pyridylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine ([LnL(tta)2]·NO3 and [LnL(tta)2(H2O)]·CF3SO3, where tta = 2-thenoyltrifluoroacetylacetonate) has been synthesized and characterized from a spectroscopic point of view, using a chiroptical technique such as electronic circular dichroism (ECD) and circularly polarized luminescence (CPL). In all cases, both ligands are capable of sensitizing the luminescence of both metal ions upon absorption of light around 280 and 350 nm. Despite small differences in the total luminescence (TL) and ECD spectra, the CPL activity of the complexes is strongly influenced by a concurrent effect of the solvent and counterion. This particularly applies to europium(III) complexes where the CPL spectra in acetonitrile can be described as a weighed linear combination of the CPL spectra in dichloromethane and methanol, which show nearly opposite signatures when their ligand stereochemistries are the same. This phenomenon could be related to the presence of equilibria interconverting solvated, anion-coordinated complexes and isomers differing by the relative orientation of the tta ligands. The difference between some bond lengths (M-N bonds, in particular) in the different species could be at the basis of such an unusual CPL activity.

| S-EPMC7997384 | biostudies-literature

Enhanced Circularly Polarized Luminescence Activity in Chiral Platinum(II) Complexes With Bis- or Triphenylphosphine Ligands.

Project description:Distinct circularly polarized luminescence (CPL) activity was observed in chiral (C∧N∧N)Pt(II) [(C∧N∧N) = 4,5-pinene-6'-phenyl-2,2'-bipyridine] complexes with bis- or triphenylphosphine ligands. Compared to the pseudo-square-planar geometry of chiral (C∧N∧N)Pt(II) complexes with chloride, phenylacetylene (PPV) and 2,6-dimethylphenyl isocyanide (Dmpi) ligands, the coordination configuration around the Pt(II) nucleus of chiral (C∧N∧N)Pt(II) complexes with bulk phosphine ligands is far more distorted. The geometry is straightforwardly confirmed by X-ray crystallography. The phosphines' participation enhanced the CPL signal of Pt(II) complexes profoundly, with the dissymmetry factor (g lum) up to 10-3. The distorted structures and enhanced chiroptical signals were further confirmed by time-dependent density functional theory (TD-DFT) calculations.

| S-EPMC7193082 | biostudies-literature

Circularly polarized luminescence in enantiopure europium and terbium complexes with modular, all-oxygen donor ligands.

Project description:The modular syntheses of three new octadentate, enantiopure ligands are reported, one with the bidentate chelating unit 2-hydroxyisophthalamide (IAM) and two with bidentate 1-hydroxy-2-pyridinone (1,2-HOPO) units. A new design principle is introduced for the chiral, non-racemic hexamines which constitute the central backbones for the presented class of ligands. The terbium(III) complex of the IAM ligand, as well as the europium(III) complexes of the 1,2-HOPO ligands, are synthesized and characterized by various techniques (NMR, UV, CD, luminescence spectroscopy). All species exhibit excellent stability and moderate to high luminescence efficiency (quantum yields Phi(Eu) = 0.05-0.08 and Phi(Tb) = 0.30-0.57) in aqueous solution at physiological pH. Special focus is put onto the properties of the complexes in regard to circularly polarized luminescence (CPL). The maximum luminescence dissymmetry factors (g(lum)) in aqueous solution are high with |g(lum)|(max) = 0.08-0.40. Together with the very favorable general properties (good stability, high quantum yields, long lifetimes), the presented lanthanide complexes can be considered as good candidates for analytical probes based on CPL in biologically relevant environments.

| S-EPMC2735592 | biostudies-literature

Unusual Magnetic Field Responsive Circularly Polarized Luminescence Probes with Highly Emissive Chiral Europium(III) Complexes.

Project description:Chirality is ubiquitous within biological systems where many of the roles and functions are still undetermined. Given this, there is a clear need to design and develop sensitive chiral optical probes that can function within a biological setting. Here we report the design and synthesis of magnetically responsive Circularly Polarized Luminescence (CPL) complexes displaying exceptional photophysical properties (quantum yield up to 31 % and |glum | up to 0.240) by introducing chiral substituents onto the macrocyclic scaffolds. Magnetic CPL responses are observed in these chiral EuIII complexes, promoting an exciting development to the field of magneto-optics. The |glum | of the 5 D0 → 7 F1 transition increases by 20 % from 0.222 (0 T) to 0.266 (1.4 T) displaying a linear relationship between the Δglum and the magnetic field strength. These EuIII complexes with magnetic CPL responses, provides potential development to be used in CPL imaging applications due to improved sensitivity and resolution.

| S-EPMC7821146 | biostudies-literature

Aggregation induced emission dynamic chiral europium(III) complexes with excellent circularly polarized luminescence and smart sensors.

Project description:The synthesis of dynamic chiral lanthanide complex emitters has always been difficult. Herein, we report three pairs of dynamic chiral EuIII complex emitters (R/S-Eu-R-1, R = Et/Me; R/S-Eu-Et-2) with aggregation-induced emission. In the molecular state, these EuIII complexes have almost no obvious emission, while in the aggregate state, they greatly enhance the EuIII emission through restriction of intramolecular rotation and restriction of intramolecular vibration. The asymmetry factor and the circularly polarized luminescence brightness are as high as 0.64 (5D0 → 7F1) and 2429 M-1cm-1 of R-Eu-Et-1, achieving a rare double improvement. R-Eu-Et-1/2 exhibit excellent sensing properties for low concentrations of CuII ions, and their detection limits are as low as 2.55 and 4.44 nM, respectively. Dynamic EuIII complexes are constructed by using chiral ligands with rotor structures or vibration units, an approach that opens a door for the construction of dynamic chiral luminescent materials.

| S-EPMC10994944 | biostudies-literature

Sequentially amplified circularly polarized ultraviolet luminescence for enantioselective photopolymerization.

Project description:Chiral optical materials based on circularly polarized luminescence (CPL) have emerged rapidly due to their feasible applications in diverse fields of research. However, limited to the small luminescence dissymmetry factor (glum), real application examples have rarely been reported. Here, we present a complex system, which show intense circularly polarized ultraviolet luminescence (CPUVL) with large glum value, enabling a chiral UV light triggered enantioselective polymerization. By integrating sensitized triplet-triplet annihilation upconversion and CPL, both visible-to-UV upconversion emission and upconverted circularly polarized ultraviolet luminescence (UC-CPUVL) were obtained in the systems, built of chiral annihilator R(S)-4,12-biphenyl[2,2]paracyclophane (R-/S-TP), and a thermally activated delayed fluorescence (TADF) sensitizer. After dispersing this upconversion system into room-temperature nematic liquid crystal, induced chiral nematic liquid crystal could significantly amplify the glum value (0.19) of UC-CPUVL. Further, the UC-CPUVL emission has been used to trigger the enantioselective photopolymerization of diacetylene. This work paves the way for the further development of functional application of CPL active materials.

| S-EPMC7652877 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data