Sulfoxide‐Induced Homochiral Folding of <i>ortho</i>‐Phenylene Ethynylenes (<i>o</i>‐OPEs) by Silver(I) Templating: Structure and Chiroptical Properties

Resa, Sandra; Miguel, Delia; Guisán-Ceinos, Santiago; Mazzeo, Giuseppe; Choquesillo‐Lazarte, Duane; Abbate, Sergio; Crovetto, Luis; Cárdenas, Diego J.; Carreño, M. Carmen; Ribagorda, María; Longhi, Giovanna; Mota, Antonio J.; Cienfuegos, Luı́s Álvarez de; Cuerva, Juan M.

doi:10.1002/chem.201704897

Cited by 38 publications

(39 citation statements)

References 119 publications

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“…Given the amenability of the o -phenylene backbone to TD-DFT calculations, 62 , 63 and precedents for the prediction of CD spectra 64 for helicenes 65 and aromatic foldamers, 42 , 66 we investigated the use of computational models to assign the absolute configurations of the o -phenylene backbones. The method was first validated † against an o -phenylene octamer reported by Fukushima and Aida 32 which is, to the best of our knowledge, the only example of an o -phenylene for which both the absolute configuration and CD spectrum are unambiguously known.…”

Section: Resultsmentioning

confidence: 99%

Twist sense control in terminally functionalized ortho-phenylenes

et al. 2018

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Section: Resultsmentioning

confidence: 99%

Twist sense control in terminally functionalized ortho-phenylenes

et al. 2018

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“…Finally ligand-centered CPL were casually tuned or switched by a closed shell d-block metal like Ag I or Au I . While Au I can be used to rigidify and organize organic chromophores to enhance its emission (Zhang J. et al, 2019 ), the interaction of Ag I with organic moieties provides CPL switch and ratiometric CPL probe (Reiné et al, 2018a ; Resa et al, 2018 ). Furthermore, CPL emission can be observed from nanoclusters of silver or gold in their metallic state (Kumar et al, 2017 ; Shi et al, 2017 ).…”

Section: Second- and Third-row Transition Metal Complexes For Cplmentioning

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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“…Thanks to this phenomenon, basis of the circularly polarized luminescence (CPL) spectroscopy, [2] valuable knowledge about the chirality of the excited states can be extracted. Forthis reason, CPL is usually considered as acomplementary technique to electronic circular dichroism (ECD) spectroscopy,w hich is devoted to the ground states.B esides their obvious applications into light-emitting devices, [3]- [5] several are the additional functionalities that can be assigned to CPL responsive structures,i ncluding molecular switches [6]- [9] and ratiometric probes, [10] etc. Therefore,the development of new materials behaving as chiral chromophores with intrinsic CPL response is an appealing topic within the chiroptic research area.…”

Section: Introductionmentioning

confidence: 99%

Organic Free Radicals as Circularly Polarized Luminescence Emitters

et al. 2019

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Chiroptical properties of two chiral atropisomers of propeller‐like trityl‐based radical derivatives have been analyzed. A new absolute configuration (AC) assignment has been made, according to the combination of experimental and theoretical data. In this sense, their ACs have been determined through the comparison of the Cotton effects recorded by electronic circular dichroism (ECD) with the theoretical ECD of the open shell structures obtained by TD‐DFT calculations. Finally, their circularly polarized luminescence (CPL) responses have been addressed. Remarkably, this is the first description of organic free radicals as intrinsic CPL emitters. Opposite signed CPL has been detected for each pair of conformers, with acceptable luminescent dissymmetry factors (|glum|≈0.5–0.8×10−3) considering their pure organic nature. In fact, highly efficient chiral emissions have been demonstrated, according to the comparison of |glum| with their respective absorption anisotropy factors (|gabs|). This pioneering study lays the foundations for the optimization of new magnetically active organic chiral emitters.

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Sulfoxide‐Induced Homochiral Folding of ortho‐Phenylene Ethynylenes (o‐OPEs) by Silver(I) Templating: Structure and Chiroptical Properties

Cited by 38 publications

References 119 publications

Twist sense control in terminally functionalized ortho-phenylenes

Twist sense control in terminally functionalized ortho-phenylenes

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

Organic Free Radicals as Circularly Polarized Luminescence Emitters

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