Yellow Circularly Polarized Luminescence from <i>C</i><sub>1</sub>‐Symmetrical Copper(I) Complexes

Deng, Min; Mukthar, Nishya F. M.; Schley, Nathan D.; Ung, Gaël

doi:10.1002/anie.201913672

Cited by 76 publications

(54 citation statements)

References 60 publications

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“…to retain the almost pure d-d character of the transition and (ii) an important energy gap with upper excited levels in order to prevent deleterious back inter system crossing (BISC). Because of those sophisticated conditions, the use of first-row metals is mainly restricted to closed shell ions with d 10 configuration, such as Zn II complexes showing ligand-based emission Kögel et al, 2016;Aoki et al, 2017;Reiné et al, 2018b;Maeda et al, 2019), or in Cu I complexes displaying MLCT emission (Zhang M.-M. et al, 2019;Deng et al, 2020). In the first case, the Zn II ions are responsible, upon their coordination to an organic ligand, for conformational changes affecting the optical and chiroptical properties, particularly in the CPL emission.…”

Section: Extension Toward 3d Metal Complexes the Promising Case Of Earth-abundant Chromium Centersmentioning

confidence: 99%

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

2020

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Chiral molecules are essential for the development of advanced technological applications in spintronic and photonic. The best systems should produce large circularly polarized luminescence (CPL) as estimated by their dissymmetry factor ( g lum ), which can reach the maximum values of −2 ≤ g lum ≤ 2 when either pure right- or left-handed polarized light is emitted after standard excitation. For matching this requirement, theoretical considerations indicate that optical transitions with large magnetic and weak electric transition dipole moments represent the holy grail of CPL. Because of their detrimental strong and allowed electric dipole transitions, popular chiral emissive organic molecules display generally moderate dissymmetry factors (10 −5 ≤ g lum ≤ 10 −3 ). However, recent efforts in this field show that g lum can be significantly enhanced when the chiral organic activators are part of chiral supramolecular assemblies or of liquid crystalline materials. At the other extreme, chiral Eu III - and Sm III -based complexes, which possess intra-shell parity-forbidden electric but allowed magnetic dipole transitions, have yielded the largest dissymmetry factor reported so far with g lum ~ 1.38. Consequently, 4f-based metal complexes with strong CPL are currently the best candidates for potential technological applications. They however suffer from the need for highly pure samples and from considerable production costs. In this context, chiral earth-abundant and cheap d-block metal complexes benefit from a renewed interest according that their CPL signal can be optimized despite the larger covalency displayed by d-block cations compared with 4f-block analogs. This essay thus aims at providing a minimum overview of the theoretical aspects rationalizing circularly polarized luminescence and their exploitation for the design of chiral emissive metal complexes with strong CPL. Beyond the corroboration that f–f transitions are ideal candidates for generating large dissymmetry factors, a special attention is focused on the recent attempts to use chiral Cr III -based complexes that reach values of g lum up to 0.2. This could pave the way for replacing high-cost rare earths with cheap transition metals for CPL applications.

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Section: Extension Toward 3d Metal Complexes the Promising Case Of Earth-abundant Chromium Centersmentioning

confidence: 99%

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

2020

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“…Organic materials have emerged as promising candidates owing to their easy processing, tunable chiral centers, and excellent photophysical properties 25 – 27 . Over the past few years, a lot of organic materials have been reported to exhibit CPL activity by combining the chiral units and the luminescent molecules via covalent bonds, such as transition metal complex 28 , 29 , small organic molecules 30 , 31 , and conjugated polymers 32 , 33 . However, they usually suffer from the relatively low luminescence dissymmetry factor ( g lum ), which quantifies the asymmetry degree of emission in left- and right-circularly polarized light.…”

Section: Introductionmentioning

confidence: 99%

Circularly polarized luminescence from organic micro-/nano-structures

et al. 2021

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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.

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“…[35][36][37][38] Several kinds of CPL materials have been developed based on small organic molecules,l anthanide and transition metal complexes. [39][40][41][42][43][44][45][46] However,f abricating full organic CPL polymeric materials with switchable handedness, tunable emission wavelength, and large dissymmetric factor (g lum )s till remain ag reat challenge. [40][41][42][43] Tu ning these emission properties could generate multicolor and even full color and white CPL for practical applications.…”

Section: Introductionmentioning

confidence: 99%

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

et al. 2020

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Controlling the self‐assembly morphology of π‐conjugated block copolymer is of great interesting. Herein, amphiphilic poly(3‐hexylthiophene)‐block‐poly(phenyl isocyanide)s (P3HT‐b‐PPI) copolymers composed of π‐conjugated P3HT and optically active helical PPI segments were readily prepared. Taking advantage of the crystallizable nature of P3HT and the chirality of the helical PPI segment, crystallization‐driven asymmetric self‐assembly (CDASA) of the block copolymers lead to the formation of single‐handed helical nanofibers with controlled length, narrow dispersity, and well‐defined helicity. During the self‐assembly process, the chirality of helical PPI was transferred to the supramolecular assemblies, giving the helical assemblies large optical activity. The single‐handed helical assemblies of the block copolymers exhibited interesting white‐light emission and circularly polarized luminescence (CPL). The handedness and dissymmetric factor of the induced CPL can be finely tuned through the variation on the helicity and length of the helical nanofibers.

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Yellow Circularly Polarized Luminescence from C₁‐Symmetrical Copper(I) Complexes

Cited by 76 publications

References 60 publications

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

Circularly polarized luminescence from organic micro-/nano-structures

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

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Yellow Circularly Polarized Luminescence from C1‐Symmetrical Copper(I) Complexes

Cited by 76 publications

References 60 publications

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

Circularly polarized luminescence from organic micro-/nano-structures

Crystallization‐Driven Asymmetric Helical Assembly of Conjugated Block Copolymers and the Aggregation Induced White‐light Emission and Circularly Polarized Luminescence

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Yellow Circularly Polarized Luminescence from C₁‐Symmetrical Copper(I) Complexes