Modular Synthesis, Orthogonal Post‐Functionalization, Absorption, and Chiroptical Properties of Cationic [6]Helicenes

Torricelli, Franck; Bosson, Johann; Besnard, Céline; Chekini, Mahshid; Bürgi, Thomas; Lacour, Jérôme

doi:10.1002/anie.201208926

Cited by 95 publications

(97 citation statements)

References 60 publications

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“…[ 1 ] , [ 2 ] Their preparation involves five straightforward steps to reach a common late-stage intermediate and then divergent procedures to afford the final products. [ 3 ] Compounds 1 - 3 are effective chromophores and can be isolated as single enantiomers ( M or P configurations).…”

Section: Introductionmentioning

confidence: 99%

Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence

Bosson

Labrador

Pascal

et al. 2016

Chemistry A European J

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Physicochemical properties of cationic dioxa 1, azaoxa 2 and diaza 3 [6]helicenes demonstrate a much higher chemical stability of diaza adduct 3 (pKR+ 20.4, E1false/2red −0.72 V) compared to azaoxa 2 (pKR+ 15.2, E1false/2red −0.45 V) and dioxa 1 (pKR+ 8.8, E1false/2red −0.12 V) analogues. The fluorescence of these cationic chromophores was established and ranges from the orange to the far-red regions. From 1 to 3, a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31% and 9.8 ns at 658 nm) are observed. The triplet quantum yields and the circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6]helicene core was achieved through selective and orthogonal post-functionalization reactions (12 examples, compounds 4-15). The electronic absorption is modulated from the orange to far-red spectral range (560-731 nm) while fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70% (619 nm). The influence of the peripheral auxochrome substituents is rationalized by first-principles calculations.

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Section: Introductionmentioning

confidence: 99%

Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence

Bosson

Labrador

Pascal

et al. 2016

Chemistry A European J

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“…Helicenes are polycyclic aromatic compounds consisting of ortho-fused benzene rings with C 2 -symmetric axis perpendicular to the axis of helicity as a result of the steric repulsive interaction between terminal aromatic rings [1][2][3]. This makes them chiral even though they have no center of chirality.…”

Section: Introductionmentioning

confidence: 99%

Experimental and theoretical study on cation–π interaction of Ag+ with [6]helicene

et al. 2015

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By employing electrospray ionization mass spectrometry, it was proven experimentally that the [6]helicene-Ag ? complex (i.e., [Ag(C 26 H 16 )] ? ) exists in the gas phase. Further, applying quantum mechanical DFT calculations, the most probable structure of this cationic complex [Ag(C 26 H 16 )] ? was derived. Finally, in the solid state, the complex [6]helicene-silver triflate-monohydrate (i.e., C 26 H 16 -AgCF 3 SO 3 -H 2 O), crystallizing in the monoclinic system with the centro-symmetric P2 1 /c space group, was prepared and analyzed. The characteristic feature of this complex packing in the solid state is the formation of the separated [6]helicene and silver triflate domains. In both of these binding modes, the investigated [6]helicene ligand functions as a molecular tweezer for the univalent silver cation. Graphical abstract Electronic supplementary material The online version of this article (

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“…C 2 -symmetric axis perpendicular to the axis of helicity as a result of the steric repulsive interaction between terminal aromatic rings [14][15][16]. This makes them chiral even though they have no center of chirality.…”

Section: Introductionmentioning

confidence: 99%

[6]Helicene as a novel molecular tweezer for the univalent silver cation: Experimental and theoretical study

Klepetářová

Makrlík

Dytrtová

et al. 2015

Journal of Molecular Structure

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Modular Synthesis, Orthogonal Post‐Functionalization, Absorption, and Chiroptical Properties of Cationic [6]Helicenes

Cited by 95 publications

References 60 publications

Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence

Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence

Experimental and theoretical study on cation–π interaction of Ag+ with [6]helicene

[6]Helicene as a novel molecular tweezer for the univalent silver cation: Experimental and theoretical study

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