Design and enantioselective synthesis of 3D π-extended carbohelicenes for circularly polarized luminescence

Wang, X., Ma, S., Zhao, B. & Deng, J. Frontiers in circularly polarized phosphorescent materials. Adv. Funct. Mater. 33, 2214364 (2023). 10.1002/adfm.202214364

[2]

Xu, H., Ma, C.-S., Yu, C.-Y., Tong, F. & Qu, D.-H. Reversible inversion of circularly polarized luminescence in a coassembly supramolecular structure with achiral sulforhodamine b dyes. ACS Appl. Mater. Interfaces 15, 25201–25211 (2023). 10.1021/acsami.2c22349

[3]

Schadt, M. Liquid crystal materials and liquid crystal displays. Annu. Rev. Mater. Sci. 27, 305–379 (1997). 10.1146/annurev.matsci.27.1.305

[4]

Sherson, J. F. et al. Quantum teleportation between light and matter. Nature 443, 557–560 (2006). 10.1038/nature05136

[5]

Sánchez-Carnerero, E. M. et al. Circularly polarized luminescence from simple organic molecules. Chem. Eur. J. 21, 13488–13500 (2015). 10.1002/chem.201501178

[6]

Quantifying the Overall Efficiency of Circularly Polarized Emitters

Lorenzo Arrico, Lorenzo Di Bari, Francesco Zinna

Chemistry – A European Journal 2021 10.1002/chem.202002791

[7]

Nakai, Y., Mori, T. & Inoue, Y. Theoretical and experimental studies on circular dichroism of carbo[n]helicenes. J. Phys. Chem. A 116, 7372–7385 (2012). 10.1021/jp304576g

[8]

One‐Step Synthesis of [16]Helicene

Kazuyuki Mori, Takashi Murase, Makoto Fujita

Angewandte Chemie International Edition 2015 10.1002/anie.201502436

[9]

Liu, W., Qin, T., Xie, W. & Yang, X. Catalytic enantioselective synthesis of helicenes. Chem. Eur. J. 28, e202202369 (2022). 10.1002/chem.202202369

[10]

Wang, Y., Wu, Z.-G. & Shi, F. Advances in catalytic enantioselective synthesis of chiral helicenes and helicenoids. Chem. Catal. 2, 3077–3111 (2022). 10.1016/j.checat.2022.10.011

[11]

Grandbois, A. & Collins, S. K. Enantioselective synthesis of [7]helicene: dramatic effects of olefin additives and aromatic solvents in asymmetric olefin metathesis. Chem. Eur. J. 14, 9323–9329 (2008). 10.1002/chem.200801033

[12]

Jančařík, A. et al. Rapid access to dibenzohelicenes and their functionalized derivatives. Angew. Chem. Int. Ed. 52, 9970–9975 (2013). 10.1002/anie.201301739

[13]

González-Fernández, E. et al. Enantioselective synthesis of [6]carbohelicenes. J. Am. Chem. Soc. 139, 1428–1431 (2017). 10.1021/jacs.6b12443

[14]

Yamano, R., Shibata, Y. & Tanaka, K. Synthesis of single and double dibenzohelicenes by rhodium-catalyzed intramolecular [2+2+2] and [2+1+2+1] cycloaddition. Chem. Eur. J. 24, 6364–6370 (2018). 10.1002/chem.201706008

[15]

Satoh, M., Shibata, Y. & Tanaka, K. Enantioselective synthesis of fully benzenoid single and double carbohelicenes via gold-catalyzed intramolecular hydroarylation. Chem. Eur. J. 24, 5434–5438 (2018). 10.1002/chem.201800986

[16]

Jia, S., Li, S., Liu, Y., Qin, W. & Yan, H. Enantioselective control of both helical and axial stereogenic elements though an organocatalytic approach. Angew. Chem. Int. Ed. 58, 18496–18501 (2019). 10.1002/anie.201909214

[17]

Yubuta, A. et al. Enantioselective synthesis of triple helicenes by cross-cyclotrimerization of a helicenyl aryne and alkynes via dynamic kinetic resolution. J. Am. Chem. Soc. 142, 10025–10033 (2020). 10.1021/jacs.0c01723

[18]

Guo, S.-M. et al. A C–H activation-based enantioselective synthesis of lower carbo[n]helicenes. Nat. Chem. 15, 872–880 (2023). 10.1038/s41557-023-01174-5

[19]

Rulíšek, L. et al. On the convergence of the physicochemical properties of [n]helicenes. J. Phys. Chem. C 111, 14948–14955 (2007). 10.1021/jp075129a

[20]

Sehnal, P. et al. An organometallic route to long helicenes. Proc. Natl Acad. Sci. USA 106, 13169–13174 (2009). 10.1073/pnas.0902612106

[21]

Shoji, Y. et al. Boron-mediated sequential alkyne insertion and C–C coupling reactions affording extended π-conjugated molecules. Nat. Commun. 7, 12704 (2016). 10.1038/ncomms12704

[22]

Kiel, G. R. et al. Expanded helicenes: a general synthetic strategy and remarkable supramolecular and solid-state behavior. J. Am. Chem. Soc. 139, 18456–18459 (2017). 10.1021/jacs.7b10902

[23]

Nakakuki, Y., Hirose, T. & Matsuda, K. Synthesis of a helical analogue of kekulene: a flexible π-expanded helicene with large helical diameter acting as a soft molecular spring. J. Am. Chem. Soc. 140, 15461–15469 (2018). 10.1021/jacs.8b09825

[24]

Fujise, K., Tsurumaki, E., Wakamatsu, K. & Toyota, S. Construction of helical structures with multiple fused anthracenes: structures and properties of long expanded helicenes. Chem. Eur. J. 27, 4548–4552 (2021). 10.1002/chem.202004720

[25]

Suárez-Pantiga, S. et al. In-Fjord substitution in expanded helicenes: effects of the Insert on the inversion barrier and helical pitch. Chem. Eur. J. 27, 13358–13366 (2021). 10.1002/chem.202102585

[26]

Zheng, W., Ikai, T., Oki, K. & Yashima, E. Consecutively fused single-, double-, and triple-expanded helicenes. Nat. Sci. 2, e20210047 (2022). 10.1002/ntls.20210047

[27]

Kiel, G. R. et al. Expanded [23]-helicene with exceptional chiroptical properties via an iterative ring-fusion strategy. J. Am. Chem. Soc. 144, 23421–23427 (2022). 10.1021/jacs.2c09555

[28]

Huo, G.-F. et al. Facile synthesis and chiral resolution of expanded helicenes with up to 35 cata-fused benzene rings. Angew. Chem. Int. Ed. 62, e202218090 (2023). 10.1002/anie.202218090

[29]

Toya, M. et al. Expanded [2,1][n]carbohelicenes with 15- and 17-benzene rings. J. Am. Chem. Soc. 145, 11553–11565 (2023). 10.1021/jacs.3c00109

[30]

Kubo, H. et al. Tuning transition electric and magnetic dipole moments: [7]helicenes showing intense circularly polarized luminescence. J. Phys. Chem. Lett. 12, 686–695 (2021). 10.1021/acs.jpclett.0c03174

[31]

Donckt, E. V., Nasielski, J., Greenleaf, J. R. & Birks, J. B. Fluorescence of the helicenes. Chem. Phys. Lett. 2, 409–410 (1968). 10.1016/0009-2614(68)80041-7

[32]

Sapir, M. & Donckt, E. V. Intersystem crossing in the helicenes. Chem. Phys. Lett. 36, 108–110 (1975). 10.1016/0009-2614(75)85698-3

[33]

Dhbaibi, K., Favereau, L. & Crassous, J. Enantioenriched helicenes and helicenoids containing main-group elements (B, Si, N, P). Chem. Rev. 119, 8846–8953 (2019). 10.1021/acs.chemrev.9b00033

[34]

Chiroptical Properties of Symmetric Double, Triple, and Multiple Helicenes

Tadashi Mori

Chemical Reviews 2021 10.1021/acs.chemrev.0c01017

[35]

Chen, X.-Y., Li, J.-K. & Wang, X.-Y. Recent advances in the syntheses of helicene-based molecular nanocarbons via the Scholl reaction. Chin. J. Org. Chem. 41, 4105–4137 (2021). 10.6023/cjoc202107063

[36]

Zhang, Y., Pun, S. H. & Miao, Q. The Scholl reaction as a powerful tool for synthesis of curved polycyclic aromatics. Chem. Rev. 122, 14554–14593 (2022). 10.1021/acs.chemrev.2c00186

[37]

Luo, J., Xu, X., Mao, R. & Miao, Q. Curved polycyclic aromatic molecules that are π-isoelectronic to hexabenzocoronene. J. Am. Chem. Soc. 134, 13796–13803 (2012). 10.1021/ja3054354

[38]

Fujikawa, T., Segawa, Y. & Itami, K. Synthesis, structures, and properties of π-extended double helicene: a combination of planar and nonplanar π-systems. J. Am. Chem. Soc. 137, 7763–7768 (2015). 10.1021/jacs.5b03118

[39]

Hu, Y. et al. Benzo-fused double [7]carbohelicene: synthesis, structures, and physicochemical properties. Angew. Chem. Int. Ed. 56, 3374–3378 (2017). 10.1002/anie.201610434

[40]

Zhu, Y. et al. Synthesis and characterization of hexapole [7]helicene, a circularly twisted chiral nanographene. J. Am. Chem. Soc. 140, 4222–4226 (2018). 10.1021/jacs.8b01447

[41]

Nakakuki, Y., Hirose, T., Sotome, H., Miyasaka, H. & Matsuda, K. Hexa-peri-hexabenzo[7]helicene: homogeneously π-extended helicene as a primary substructure of helically twisted chiral graphenes. J. Am. Chem. Soc. 140, 4317–4326 (2018). 10.1021/jacs.7b13412

[42]

Cruz, C. M., Castro-Fernández, S., Maçôas, E., Cuerva, J. M. & Campaña, A. G. Undecabenzo[7]superhelicene: a helical nanographene ribbon as a circularly polarized luminescence emitter. Angew. Chem. Int. Ed. 57, 14782–14786 (2018). 10.1002/anie.201808178

[43]

Zhu, Y., Guo, X., Li, Y. & Wang, J. Fusing of seven HBCs toward a green nanographene propeller. J. Am. Chem. Soc. 141, 5511–5517 (2019). 10.1021/jacs.9b01266

[44]

Cruz, C. M. et al. A triskelion-shaped saddle-helix hybrid nanographene. Angew. Chem. Int. Ed. 58, 8068–8072 (2019). 10.1002/anie.201902529

[45]

Hu, Y. et al. π-Extended pyrene-fused double [7]carbohelicene as a chiral polycyclic aromatic hydrocarbon. J. Am. Chem. Soc. 141, 12797–12803 (2019). 10.1021/jacs.9b05610

[46]

Guo, X. et al. A nitrogen-doped hexapole [7]helicene versus its all-carbon analogue. Angew. Chem. Int. Ed. 58, 16966–16972 (2019). 10.1002/anie.201907972

[47]

Chen, Y. et al. Double π-extended undecabenzo[7]helicene. Angew. Chem. Int. Ed. 60, 7796–7801 (2021). 10.1002/anie.202014621

[48]

Yao, X. et al. Synthesis of nonplanar graphene nanoribbon with fjord edges. J. Am. Chem. Soc. 143, 5654–5658 (2021). 10.1021/jacs.1c01882

[49]

Pun, S. H. et al. A near-infrared absorbing and emissive quadruple helicene enabled by the Scholl reaction of perylene. Angew. Chem. Int. Ed. 61, e202113203 (2022). 10.1002/anie.202113203

[50]

Xu, X. et al. Synthesis of bioctacene-incorporated nanographene with near-infrared chiroptical properties. Angew. Chem. Int. Ed. 62, e202218350 (2023). 10.1002/anie.202218350

Showing 50 of 66 references

Cited By

67

Selective and Divergent Synthesis of Naphthalene‐ and Phenanthrene‐Fused Azahelicenes by Turning Rearrangement On or Off

Chihiro Maeda, Sayaka Michishita · 2025

Chemistry – A European Journal

π‐Extended Heli(aminoborane)s with Highly Bright Circularly Polarized Luminescence and Narrowband Emission

Yang Yu, Chang Wang · 2025

Angewandte Chemie International Edi...

Symmetry‐Engineered Ultralong Phosphorescence in Double π‐Helical Nanographenes

Yujian Liu, Xu Wen · 2025

Angewandte Chemie

Laterally π-Extended Polyhelicenes

Hao Wu, Zijie Qiu · 2025

Journal of the American Chemical So...

Benzo-Extended Heli(aminoborane)s: Inner Rim BN-Doped Helical Molecular Carbons with Remarkable Chiroptical Properties

Yang Yu, Chang Wang · 2024

Journal of the American Chemical So...

Perylene‐Embedded Helical Nanographenes with Emission up to 1010 nm: Synthesis, Structures, and Chiroptical Properties

Gui‐Fei Huo, Wei‐Tao Xu · 2024

Angewandte Chemie

Enantiomerically Pure Helical Bilayer Nanographenes: A Straightforward Chemical Approach

Patricia Izquierdo-García, Jesús M. Fernández-García · 2024

Journal of the American Chemical So...

Metrics

67

Citations

66

References

Details

Published: Apr 19, 2024
Vol/Issue: 3(6)
Pages: 774-786
License: View

Authors

Department of Chemical Science and Engineering Tokyo Institute of Technology O-okayama, Meguro-ku Tokyo 152-8550 Japan

Department of Orthopedic Surgery, Graduate School of Medicine, Chiba University, Chiba, Japan.

Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan; Research Initiative for Supra-Materials (RISM), Shinshu University, 3-15-1 Tokita, Ueda, Japan

H

Hidehiro Uekusa

Institute of Science Tokyo

K

Ken Tanaka

Funding

MEXT | Japan Science and Technology Agency Award: JPMJFS2112

Cite This Article

Futo Morita, Yuko Kishida, Yu Sato, et al. (2024). Design and enantioselective synthesis of 3D π-extended carbohelicenes for circularly polarized luminescence. Nature Synthesis, 3(6), 774-786. https://doi.org/10.1038/s44160-024-00527-3

Design and enantioselective synthesis of 3D π-extended carbohelicenes for circularly polarized luminescence

You May Also Like