Pyrene magic: chiroptical enciphering and deciphering 1,3-dioxolane bearing two wirepullings to drive two remote pyrenes

Amako, Tomoyuki; Nakabayashi, Kazuki; Suzuki, Nozomu; Guo, Sibo; Rahim, Nor Azura Abdul; Harada, Takunori; Fujiki, Michiya; Imai, Yoshitane

doi:10.1039/c5cc01465d

Cited by 45 publications

(21 citation statements)

References 53 publications

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“…Opticallya ctive, emissive, conjugated compounds exhibit ap otential differenceb etween their left-and right-handedc ircularly polarized luminescence (CPL [1] )i ntensities. Recently,t he development of optically active CPL-emitting organic compounds [2][3][4][5][6][7][8][9][10][11] for applicationsi n3 Dorganicl ight-emitting devices has received much attention.C PL characteristics are evaluated from the photoluminescence (PL)i ntensity and the luminescence dissymmetry factor (g lum ), defined as 2(I left ÀI right )/ (I left + I right ), in which I left and I right represent the left-and right-handedC PL intensities, respectively.T he molara bsorption coefficient (e), PL quantum efficiency (F lum ), and large g lum value are therefore important factorsi nC PL materials.H owever,i ti s generally difficult to achieve large PL intensities in combination with large g lum values due to the existing challenges in obtaining large g lum values in organic compounds.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Optically Active, X‐Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence

Gon

Morisaki

Sawada

et al. 2016

Chemistry A European J

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What promoted you to investigate this topic/problem? We achieved practical optical resolution of planar chiral 4,12-disub-stituted and 4,7,12,15-tetrasubstituted [2.2]paracyclophane compounds in 2012 and 2014, respectively.W eh ave prepared various conjugated compounds consisting of the di-or tetrasubstituted planar chiral [2.2]paracyclophane units. These compounds emit intense circularly polarized luminescence (CPL) with high photolumi-nescence (PL) quantum efficiencyinsolution, whereas the PL quantum efficiencyd ecreases dramatically in the solid state. We tried to overcome the problem of aggregation-caused quenching and obtain CPL-emissive thin films by taking advantage of ad endritic structure. What is the most significant result of this study? We could solve the above-mentioned problem completely;n amely, we achieved intense CPL from the dendrimer thin films with high PL quantum efficiencies. The dendrons sufficiently isolate the planar chiral [2.2]paracyclophane-containing conjugated core unit; this suppresses the aggregation-caused quenching of the core. In addition, the dendrons show al ight-harvesting effect and provide film-forming ability.T hus, the dendrimer films exhibited large molar extinction coefficients, high PL quantum efficiencies, intense PL and CPL, and large CPL dissymmetry factors. We realized gram-scale optical resolution and transformations of 4,7,12,15-tetrasub-stituted [2.2]paracyclophanes in this study. What other topics are you working on at the moment? We have been interested in "chirality". In particular,w eh ave fo-cused on the central chirality of the phosphorus atom in addition to the planar chirality of [2.2]paracyclophane. It is well known that the trivalent phosphorus atom in phosphine can act as ac hiral center because of the high inversion energy,u nlike that of nitrogen atoms. From this viewpoint, we have focused on P-chiral phos-phines and synthesized optically active P-chiral polymers, oligo-mers, and cyclic compounds using P-stereogenic bisphosphines as chiral building blocks. Recently,apractical synthetic route to P-ste-reogenic diphosphacrowns (crown ether derivatives consisting of chiral phosphorus atoms in the ring skeletons) was developed. Syntheses of various P-stereogenic phosphacrowns, investigations on the host-guest chemistry,a nd attempts for application to the field of materials chemistry are underway. Invited for the cover of this issue is YasuhiroM orisaki at Kwansei Gakuin University together with the group of Yoshiki Chujo at Kyoto University.T he image depicts the circularly polarizedl uminescence of the dendrimer films described in their Full Paper.R ead the full text of the article at

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Section: Introductionmentioning

confidence: 99%

Synthesis of Optically Active, X‐Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence

Gon

Morisaki

Sawada

et al. 2016

Chemistry A European J

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“…Aiming at designing more elaborate active function, e.g., photon-induced chirality in the photoexcited state, followed by spontaneous relaxation process to restore the ground-state chirality, [4][5][6][7] the choice of the opposite and/or same signs in the ground-state and photoexcited-state molecular chiralities can be exploited as advanced security systems for future global communication. 1c In this case, CD sign at the first Cotton band (a longer wavelength edge) is identical to CPL sign at the first Cotton band (a shorter wavelength edge).…”

Section: Resultsmentioning

confidence: 99%

Photoexcited state chirality transfer. Hidden tunability of circularly polarized luminescent binaphthyl–anthracene tandem molecular systems

et al. 2015

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“…Quite often, small nonchromophoric molecules show weak or negligible optical rotation, making the use of this technique also challenging . Moreover, some molecules may be CD silent and display very little or no optical rotation even in the presence of chromophores . This phenomenon is indicated as cryptochirality.…”

Section: Methodsmentioning

confidence: 99%

“…8 Moreover, some molecules may be CD silent and display very little or no optical rotation 3,9 even in the presence of chromophores. [10][11][12] This phenomenon is indicated as cryptochirality. When such situations occur, vibrational circular dichroism (VCD) may prove a powerful and relatively easy tool to assess absolute configurations and even support relative configurations determined with other methods.…”

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confidence: 99%

Towards the Limits of Vibrational Circular Dichroism Spectroscopy: VCD Spectra of Some Alkyl Vinylethers

Zinna

2015

Chirality

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Three alkyl vinylethers from our collection of chiral samples were investigated through VCD spectroscopy, in combination with Density Functional Theory (DFT) calculations. Despite the simplicity of the compounds, reproducing all the spectral features is an involved task, since the many significantly populated conformers contribute to the total VCD spectrum with bands which often have opposite signatures. Nevertheless, we show that certain bands can be satisfactorily reproduced by calculation and therefore they may be employed for the determination of absolute configuration in these and similar compounds, for which no simple alternative method is available.

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Pyrene magic: chiroptical enciphering and deciphering 1,3-dioxolane bearing two wirepullings to drive two remote pyrenes

Cited by 45 publications

References 53 publications

Synthesis of Optically Active, X‐Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence

Synthesis of Optically Active, X‐Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence

Photoexcited state chirality transfer. Hidden tunability of circularly polarized luminescent binaphthyl–anthracene tandem molecular systems

Towards the Limits of Vibrational Circular Dichroism Spectroscopy: VCD Spectra of Some Alkyl Vinylethers

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