Lanthanide Circularly Polarized Luminescence: Bases and Applications

Zinna, Francesco; Bari, Lorenzo Di

doi:10.1002/chir.22382

Cited by 442 publications

(415 citation statements)

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“…Very recently, circularly polarized luminescence (CPL) has gained attention as a next-generation light source because of its distinct advantages of including extensive optical information and not being angularly dependent. Possible applications are expected in advanced optical technologies, including stereopsis, 2 optical recording, 3 molecular sensing, 4 and optical security systems. 5 CPL can be generated by chiral fluorophores, and the dissymmetry factor (g lum ) 6 is considered important in the evaluation of CPL characteristics.…”

mentioning

confidence: 99%

Facile and Versatile Approach for Generating Circularly Polarized Luminescence by Non-chiral, Low-molecular Dye-on-nanotemplate Composite System

et al. 2016

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This paper proposes a new approach for generating strong circularly polarized luminescence (CPL), based on the complexation of non-chiral, non-functionalized fluorophores with chirallyassembled nanotemplate. The observed CPL intensities of anthracene and pyrene bound to the nanotemplate reached ¹1.4 © 10 ¹2 and ¹0.85 © 10 ¹2 (dissymmetry factor), respectively. 10¹2 have been achieved for several chiral organic molecules.11 However, these systems are mainly developed through complicated synthetic chemical approaches, which not only lead to high cost of production, but also introduce some limitations in diversifying the molecular structures and CPL characteristics.To overcome these issues, we propose herein a newly developed supramolecular approach, in which non-chiral and non-functionalized fluorophores are bound to chirally-assembled nanotemplates to cause induced CPL (i-CPL), as shown in Figure 1. This supramolecular approach has the following advantages. (1) Chirality is not required in the fluorophore components; therefore, fewer limitations arise in their synthesis. Simple fluorophores, such as anthracene and pyrene, can be used because of such an advantage. (2) As a chiral source, a chiral lipid bilayer membrane system is used. Therefore, a secondary chirality, which is larger than the molecular chirality, 12,13 can be induced into the incorporated fluorophores. (3) Large «g lum « values can be achieved by simply mixing the two components, and the emission region for CPL can also be tuned by selecting an appropriate fluorophore.In this study, G-Py + as a chiral amphiphile ( Figure S1, SI) was selected for a chiral nanotemplate because G-Py + formed nanofibrillar aggregates with highly ordered chirality.13a,13b,14 The G-Py + nanotemplate with fluorophores was prepared as follows: G-Py + and pyrene were dissolved in chloroform in a molar ratio of 40:1. The chloroform solution was removed at 60°C, water was added to obtain a concentration of 0.5 mM in G-Py + , and the aqueous mixture was ultrasonicated to obtain a clear solution. This solution was heated to 90°C for 30 min, and was then cooled to 25°C to conduct various spectroscopic analyses. Using a similar procedure, other mixtures were prepared using anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, and fluorene.The G-Py + -and-pyrene mixed system formed nanofibrillar aggregates containing twisted ribbon-like aggregates at room temperature, similar to that of the system containing G-Py + alone ( Figure S2, SI). Differential scanning calorimetry (DSC) of G-Py , was observed around the absorption bands of the G-Py + carbonyl groups and pyridinium, respectively ( Figure S4, SI). These results indicate that the G-Py + nanofibrillar aggregates are formed through chirally ordered stacking in the pyridinium groups and the amide bonds.The absorption spectra of the G-Py + /pyrene mixture displayed max values at 323 and 339 nm at temperatures between 0 and 30°C (below T c ), and max values at 321 and 337 nm at temperatures higher than 50°C (above T c , Figur...

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confidence: 99%

Facile and Versatile Approach for Generating Circularly Polarized Luminescence by Non-chiral, Low-molecular Dye-on-nanotemplate Composite System

et al. 2016

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“…Circularly polarized luminescence (CPL) has drawn increasing attention [1][2][3][4][5][6] for their promising potentials in wide-ranging applications including stereopsis, [7] optical storage devices, [8] biological sensors, [9][10][11] asymmetrical catalysis and synthesis [12][13][14][15] and security systems. [16] In order to realize circularly polarized luminescence, asymmetrical environment and phosphors are essential elements.…”

Section: Circularly Polarized Luminescencementioning

confidence: 99%

Circularly Polarized Luminescent Carbon Dot Nanomaterials of Helical Superstructures for Circularly Polarized Light Detection

Zheng

Wang

et al. 2018

Advanced Optical Materials

108

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representatives of this category. [21] Early attempts to render inorganic quantum dots with chiroptical activity involve the use of chiral stabilizers. Experimental studies showed that stabilizer-modified quantum dots, such as CdS and CdTe, enabled circular dichroism, however, they were circularly polarized luminescenceinactive. [22,23] Theoretical calculations suggested that the chiral stabilizers caused distortion of the surface layer, however, the core of quantum dots remained achiral, which may explain the circularly polarized luminescence inactivity. [24] It was later hypothesized that enclosing quantum dots in a chiral environment may render quantum dots with circularly polarized luminescence activity, indeed, such a hypothesis found experimental evidences in a chiral nanostructure of apoferritin encapsulating CdS. [25] This lead to new chiral inorganic nanomaterials based on quantum dots and some novel approaches for circularly polarized luminescence generation. Representative work include CdSe quantum dots grafted with chiral cysteine, [26] CdTe nanowires embedded in stretchable twisted fibers [4] and chiral nanostructures of chalcogenide quantum dots. [27] However, these inorganic nanostructures are inadequate for applications due to their tedious synthesis procedures and low CPL strength with dissymmetry factors in the range of 10 −3 -10 −4 . It is clear that circularly polarized luminescent quantum dot nanomaterials with high strength, precise handedness, tunable wavelengths, and suitable for scale-up are highly desirable.Carbon dots are remarkable inorganic phosphors with distinct features such as tunable photoluminescence, high emission intensity, photostability, biocompatibility, and easy availability, which are superior to many inorganic quantum dots. [28][29][30][31] They are promising for bioimaging, sensing, light emitting diodes, energy storage, photocatalysis, and optoelectronic applications. [32][33][34][35][36][37][38] It can be anticipated that conferring circularly polarized luminescence on carbon dots will avail novel circularly polarized luminescent nanomaterials for biomedicine and nanoscience. Such materials, to the best of our knowledge, are not reported to date.Cellulose nanocrystals are renewable, biocompatible, and low-cost nanomaterials. They have intrinsic ability to selfassemble forming a left-handed chiral nematic organization that can be preserved upon drying. [39][40][41] Taking advantage of this property, a realm of cellulose nanocrystal-based helical Circularly polarized luminescent carbon dot nanomaterials of self-organized helical superstructures based on cellulose nanocrystals enable strong, right-handed, and multicolor tunable circularly polarized luminescence with extraordinary dissymmetry factors up to −0.74. The effects of emission intensity and carbon dots loading on the strength of the righthanded circularly polarized luminescence are experimentally observed and theoretically explained. Potentials of the carbon dots-cellulose nanomaterials for circularly polarized ...

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“…4 Driven by their long excited state lifetimes, characteristic emission, and diverse chemistry, luminescent lanthanide, Ln(III), complexes have a long history of use as molecular probes. 5,6 In particular, helical tris(dipicolinate) (dipicolinate = DPA) complexes of lanthanide cations with D 3 symmetry ([Ln(DPA) 3 ] 3− ) have been used to sense chirality of small molecules, where the racemic equilibrium between the Λ and Δ configurations of the complex is perturbed by the association of small chiral molecules in solution (figure 1). 7–15 This perturbation of a racemic equilibrium has been termed the “Pfeiffer effect”, after its discoverer.…”

Section: Introductionmentioning

confidence: 99%

“…7–15 This perturbation of a racemic equilibrium has been termed the “Pfeiffer effect”, after its discoverer. 6,16,17 …”

Section: Introductionmentioning

confidence: 99%

Localizing Perturbations of the Racemic Equilibria Involving Dipicolinate‐Derived Lanthanide(III) Complexes

2016

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Helical D3 tris(4-amino-2,6-pyridine-dicarboxylate)terbium(III) and europium(III) complexes, which form a racemic equilibrium in aqueous solution, were prepared to study their secondary coordination sphere interactions with chiral amino acids. These interactions were probed using a combination of circularly polarized luminescence (CPL) and 13C NMR spectroscopy. Results indicate that regardless of the interaction between the chiral molecule and the complex, without an accessible hydrogen-bond donor on the associating molecule, perturbation of the racemic equilibrium cannot occur. A generalized conclusion is established which indicates the mechanism of chiral recognition by tris(dipicolinate)lanthanide(III) complexes is similar across a variety of analogous ligands.

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Lanthanide Circularly Polarized Luminescence: Bases and Applications

Cited by 442 publications

References 73 publications

Facile and Versatile Approach for Generating Circularly Polarized Luminescence by Non-chiral, Low-molecular Dye-on-nanotemplate Composite System

Facile and Versatile Approach for Generating Circularly Polarized Luminescence by Non-chiral, Low-molecular Dye-on-nanotemplate Composite System

Circularly Polarized Luminescent Carbon Dot Nanomaterials of Helical Superstructures for Circularly Polarized Light Detection

Localizing Perturbations of the Racemic Equilibria Involving Dipicolinate‐Derived Lanthanide(III) Complexes

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