Chirality Amplified: Long, Discrete Helicene Nanoribbons

Xiao, Xiao; Pedersen, Stephan K.; Aranda, Daniel; Yang, Jingjing; Wiscons, Ren A.; Pittelkow, Michael; Steigerwald, Michael L.; Santoro, Fabrizio; Schuster, Nathaniel J.; Nuckolls, Colin

doi:10.1021/jacs.0c11260

Chirality Amplified: Long, Discrete Helicene Nanoribbons

Journal Article · Tue Dec 29 23:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c11260· OSTI ID:2202964

Xiao, Xiao ^[1]; Pedersen, Stephan K. ^[2]; ^[3]; ^[4]; Wiscons, Ren A. ^[4]; Pittelkow, Michael ^[5]; Steigerwald, Michael L. ^[4]; ^[6]; Schuster, Nathaniel J. ^[4]; ^[4]

Columbia University, New York, NY (United States); Columbia University
Columbia University, New York, NY (United States); University of Copenhagen (Denmark)
Universidad de Malaga (Spain); Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), Pisa (Italy)
Columbia University, New York, NY (United States)
University of Copenhagen (Denmark)
Istituto di Chimica dei Composti Organo Metallici (ICCOM-CNR), Pisa (Italy)

Here we report the synthesis of two polyhelicene frameworks consisting, from end-to-end, of 18 and 24 fused benzene rings. The latter exhibits the largest electronic circular dichroism in the visible spectrum of any molecule. These shape-persistent helical nanoribbons incorporate multiple helicenes, a class of contorted polycyclic aromatic molecules consisting of ortho-annulated rings. These conjugated, chiral molecules have interesting chemical, biological, and chiroptical properties; however, there are very few helicenes with extraordinary chiroptical response over a broad range of the visible spectrum—a key criterion for applications such as chiral optoelectronics. In this report, we show that coupling the polyhelicene framework with multiple perylene-diimide subunits elicits a significant chiroptic response. Notably, the molar circular dichroism increases faster than the absorptivity of these molecules as their helical axis lengthens. Computational analysis reveals that the greatly amplified circular dichroism arises from exciton-like interactions between the perylene-diimide and the helicene moieties. As a result, we predict that even greater chiroptic enhancement will result from further axial elongation of these nanoribbons, which can be readily enabled via the iterative synthetic method presented herein.

View Accepted Manuscript (DOE)

Research Organization:: Columbia University, New York, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); U.S. National Institutes of Health

Grant/Contract Number:: SC0019440

OSTI ID:: 2202964

Alternate ID(s):: OSTI ID: 1853250

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 2 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (52)

“Figure Eight” Cyclooctapyrroles: Enantiomeric Separation and Determination of the Absolute Configuration of a Binuclear Metal Complex Werner†, Andreas; Michels, Martin; Zander, Lars Angewandte Chemie International Edition, Vol. 38, Issue 24 https://doi.org/10.1002/(SICI)1521-3773(19991216)38:24<3650::AID-ANIE3650>3.0.CO;2-F	journal	December 1999
Helicenes-A New Class of Organic Spin Filter Kiran, Vankayala; Mathew, Shinto P.; Cohen, Sidney R. Advanced Materials, Vol. 28, Issue 10 https://doi.org/10.1002/adma.201504725	journal	January 2016
One-Step Synthesis of [16]Helicene Mori, Kazuyuki; Murase, Takashi; Fujita, Makoto Angewandte Chemie International Edition, Vol. 54, Issue 23 https://doi.org/10.1002/anie.201502436	journal	April 2015
Electron Delocalization in Perylene Diimide Helicenes Schuster, Nathaniel J.; Paley, Daniel W.; Jockusch, Steffen Angewandte Chemie International Edition, Vol. 55, Issue 43 https://doi.org/10.1002/anie.201607878	journal	September 2016
Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor Nejedlý, Jindřich; Šámal, Michal; Rybáček, Jiří Angewandte Chemie International Edition, Vol. 56, Issue 21 https://doi.org/10.1002/anie.201700341	journal	April 2017
Synthesis of a Helical Bilayer Nanographene Evans, Paul J.; Ouyang, Jiangkun; Favereau, Ludovic Angewandte Chemie International Edition, Vol. 57, Issue 23 https://doi.org/10.1002/anie.201800798	journal	March 2018
Bowls, Hoops, and Saddles: Synthetic Approaches to Curved Aromatic Molecules Majewski, Marcin A.; Stępień, Marcin Angewandte Chemie International Edition, Vol. 58, Issue 1 https://doi.org/10.1002/anie.201807004	journal	November 2018
Undecabenzo[7]superhelicene: A Helical Nanographene Ribbon as a Circularly Polarized Luminescence Emitter Cruz, Carlos M.; Castro-Fernández, Silvia; Maçôas, Ermelinda Angewandte Chemie International Edition, Vol. 57, Issue 45 https://doi.org/10.1002/anie.201808178	journal	October 2018
Nanographene Imides Featuring Dual-Core Sixfold [5]Helicenes Liu, Guogang; Koch, Tobias; Li, Yan Angewandte Chemie International Edition, Vol. 58, Issue 1 https://doi.org/10.1002/anie.201810734	journal	December 2018
A Triskelion‐Shaped Saddle–Helix Hybrid Nanographene Cruz, Carlos M.; Márquez, Irene R.; Castro‐Fernández, Silvia Angewandte Chemie International Edition, Vol. 58, Issue 24 https://doi.org/10.1002/anie.201902529	journal	May 2019
Selective Synthesis of Conjugated Chiral Macrocycles: Sidewall Segments of (−)/(+)‐(12,4) Carbon Nanotubes with Strong Circularly Polarized Luminescence Wang, Jinyi; Zhuang, Guilin; Chen, Muqing Angewandte Chemie International Edition, Vol. 59, Issue 4 https://doi.org/10.1002/anie.201909401	journal	December 2019
Stereoselective Syntheses, Structures, and Properties of Extremely Distorted Chiral Nanographenes Embedding Hextuple Helicenes Roy, Myriam; Berezhnaia, Veronika; Villa, Marco Angewandte Chemie International Edition, Vol. 59, Issue 8 https://doi.org/10.1002/anie.201913200	journal	February 2020
Recent Progress in Chemistry of Multiple Helicenes Li, Changqing; Yang, Yong; Miao, Qian Chemistry - An Asian Journal, Vol. 13, Issue 8 https://doi.org/10.1002/asia.201800073	journal	March 2018
Speciation Control During Suzuki-Miyaura Cross-Coupling of Haloaryl and Haloalkenyl MIDA Boronic Esters Fyfe, James W. B.; Valverde, Elena; Seath, Ciaran P. Chemistry - A European Journal, Vol. 21, Issue 24 https://doi.org/10.1002/chem.201500970	journal	May 2015
Porphyrin-Based Air-Stable Helical Radicals Kato, Kenichi; Furukawa, Ko; Mori, Tadashi Chemistry - A European Journal, Vol. 24, Issue 3 https://doi.org/10.1002/chem.201705291	journal	December 2017
Chiral multifunctional molecules based on organometallic helicenes: Recent advances OuYang, Jiangkun; Crassous, Jeanne Coordination Chemistry Reviews, Vol. 376 https://doi.org/10.1016/j.ccr.2018.08.015	journal	December 2018
Helicene-based chiroptical switches Isla, Helena; Crassous, Jeanne Comptes Rendus Chimie, Vol. 19, Issue 1-2 https://doi.org/10.1016/j.crci.2015.06.014	journal	January 2016
Perylene Bisimide Dye Assemblies as Archetype Functional Supramolecular Materials Würthner, Frank; Saha-Möller, Chantu R.; Fimmel, Benjamin Chemical Reviews, Vol. 116, Issue 3 https://doi.org/10.1021/acs.chemrev.5b00188	journal	August 2015
Main-Group-Based Electro- and Photoactive Chiral Materials Pop, Flavia; Zigon, Nicolas; Avarvari, Narcis Chemical Reviews, Vol. 119, Issue 14 https://doi.org/10.1021/acs.chemrev.8b00770	journal	April 2019
Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P) Dhbaibi, Kais; Favereau, Ludovic; Crassous, Jeanne Chemical Reviews, Vol. 119, Issue 14 https://doi.org/10.1021/acs.chemrev.9b00033	journal	July 2019
Laterally π-Extended Dithia[6]helicenes with Heptagons: Saddle-Helix Hybrid Molecules Fujikawa, Takao; Segawa, Yasutomo; Itami, Kenichiro The Journal of Organic Chemistry, Vol. 82, Issue 15 https://doi.org/10.1021/acs.joc.7b01540	journal	July 2017
Functionalized Helical Building Blocks for Nanoelectronics Khokhlov, Khrystofor; Schuster, Nathaniel J.; Ng, Fay Organic Letters, Vol. 20, Issue 7 https://doi.org/10.1021/acs.orglett.8b00541	journal	March 2018
Helicene-SPP-Based Chiral Plasmonic Hybrid Structure: Toward Direct Enantiomers SERS Discrimination Kalachyova, Yevgeniya; Guselnikova, Olga; Elashnikov, Roman ACS Applied Materials & Interfaces, Vol. 11, Issue 1 https://doi.org/10.1021/acsami.8b15520	journal	December 2018
Helicenes: Synthesis and Applications Shen, Yun; Chen, Chuan-Feng Chemical Reviews, Vol. 112, Issue 3 https://doi.org/10.1021/cr200087r	journal	October 2011
Benchmarking Time-Dependent Density Functional Theory for Excited State Geometries of Organic Molecules in Gas-Phase and in Solution Guido, Ciro A.; Knecht, Stefan; Kongsted, Jacob Journal of Chemical Theory and Computation, Vol. 9, Issue 5 https://doi.org/10.1021/ct400021c	journal	April 2013
Highly Enhanced Bisignate Circular Dichroism of Ferrocene-Bridged Zn(II) Bisporphyrin Tweezer with Extended Chiral Substrates due to Well-Matched Host–Guest System Brahma, Sanfaori; Ikbal, Sk Asif; Dhamija, Avinash Inorganic Chemistry, Vol. 53, Issue 5 https://doi.org/10.1021/ic401395d	journal	February 2014
Marked Effect of Aromatic Solvent on Unfolding Rate of Helical Ethynylhelicene Oligomer Sugiura, Hiroki; Nigorikawa, Yasuko; Saiki, Yuto Journal of the American Chemical Society, Vol. 126, Issue 45 https://doi.org/10.1021/ja0478882	journal	November 2004
Enantioselective Synthesis and Enhanced Circularly Polarized Luminescence of S-Shaped Double Azahelicenes Nakamura, Kyosuke; Furumi, Seiichi; Takeuchi, Masayuki Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja500841f	journal	April 2014
The Structural Origins of Intense Circular Dichroism in a Waggling Helicene Nanoribbon Schuster, Nathaniel J.; Joyce, Leo A.; Paley, Daniel W. Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00646	journal	April 2020
Perylene Diimide-Embedded Double [8]Helicenes Liu, Bo; Böckmann, Marcus; Jiang, Wei Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00954	journal	March 2020
Chiral Nanographene Propeller Embedding Six Enantiomerically Stable [5]Helicene Units Berezhnaia, Veronika; Roy, Myriam; Vanthuyne, Nicolas Journal of the American Chemical Society, Vol. 139, Issue 51 https://doi.org/10.1021/jacs.7b07622	journal	October 2017
Expanded Helicenes: A General Synthetic Strategy and Remarkable Supramolecular and Solid-State Behavior Kiel, Gavin R.; Patel, Sajan C.; Smith, Patrick W. Journal of the American Chemical Society, Vol. 139, Issue 51 https://doi.org/10.1021/jacs.7b10902	journal	December 2017
Hexa- peri -hexabenzo[7]helicene: Homogeneously π-Extended Helicene as a Primary Substructure of Helically Twisted Chiral Graphenes Nakakuki, Yusuke; Hirose, Takashi; Sotome, Hikaru Journal of the American Chemical Society, Vol. 140, Issue 12 https://doi.org/10.1021/jacs.7b13412	journal	February 2018
Synthesis and Characterization of Hexapole [7]Helicene, A Circularly Twisted Chiral Nanographene Zhu, Yanpeng; Xia, Zeming; Cai, Zeying Journal of the American Chemical Society, Vol. 140, Issue 12 https://doi.org/10.1021/jacs.8b01447	journal	February 2018
A Helicene Nanoribbon with Greatly Amplified Chirality Schuster, Nathaniel J.; Hernández Sánchez, Raúl; Bukharina, Daria Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b03535	journal	May 2018
5,14-Diaryldiindeno[2,1- f :1′,2′ -j ]picene: A New Stable [7]Helicene with a Partial Biradical Character Hsieh, Ya-Chu; Wu, Cheng-Feng; Chen, Yi-Ting Journal of the American Chemical Society, Vol. 140, Issue 43 https://doi.org/10.1021/jacs.8b08840	journal	October 2018
Synthesis of a Helical Analogue of Kekulene: A Flexible π-Expanded Helicene with Large Helical Diameter Acting as a Soft Molecular Spring Nakakuki, Yusuke; Hirose, Takashi; Matsuda, Kenji Journal of the American Chemical Society, Vol. 140, Issue 45 https://doi.org/10.1021/jacs.8b09825	journal	October 2018
π-Extended Corannulene-Based Nanographenes: Selective Formation of Negative Curvature Fernández-García, Jesús M.; Evans, Paul J.; Medina Rivero, Samara Journal of the American Chemical Society, Vol. 140, Issue 49 https://doi.org/10.1021/jacs.8b09992	journal	November 2018
Corannurylene Pentapetalae Meng, Dong; Liu, Guogang; Xiao, Chengyi Journal of the American Chemical Society, Vol. 141, Issue 13 https://doi.org/10.1021/jacs.9b00053	journal	March 2019
Fusing of Seven HBCs toward a Green Nanographene Propeller Zhu, Yanpeng; Guo, Xiaoyu; Li, Yang Journal of the American Chemical Society, Vol. 141, Issue 13 https://doi.org/10.1021/jacs.9b01266	journal	March 2019
Theoretical and Experimental Studies on Circular Dichroism of Carbo[ n ]helicenes Nakai, Yoshito; Mori, Tadashi; Inoue, Yoshihisa The Journal of Physical Chemistry A, Vol. 116, Issue 27 https://doi.org/10.1021/jp304576g	journal	June 2012
The added value of small-molecule chirality in technological applications Brandt, Jochen R.; Salerno, Francesco; Fuchter, Matthew J. Nature Reviews Chemistry, Vol. 1, Issue 6 https://doi.org/10.1038/s41570-017-0045	journal	June 2017
Symmetry-based rational design for boosting chiroptical responses Tanaka, Hiroki; Ikenosako, Mina; Kato, Yuka Communications Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/s42004-018-0035-x	journal	July 2018
One hundred years of helicene chemistry. Part 2: stereoselective syntheses and chiral separations of carbohelicenes Gingras, Marc; Félix, Guy; Peresutti, Romain Chem. Soc. Rev., Vol. 42, Issue 3 https://doi.org/10.1039/C2CS35111K	journal	January 2013
One hundred years of helicene chemistry. Part 3: applications and properties of carbohelicenes Gingras, Marc Chem. Soc. Rev., Vol. 42, Issue 3 https://doi.org/10.1039/C2CS35134J	journal	January 2013
One hundred years of helicene chemistry. Part 1: non-stereoselective syntheses of carbohelicenes Gingras, Marc Chem. Soc. Rev., Vol. 42, Issue 3 https://doi.org/10.1039/C2CS35154D	journal	January 2013
Application of electronic circular dichroism in the study of supramolecular systems Pescitelli, Gennaro; Di Bari, Lorenzo; Berova, Nina Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00104D	journal	January 2014
Helicene-like chiral auxiliaries in asymmetric catalysis Aillard, P.; Voituriez, A.; Marinetti, A. Dalton Trans., Vol. 43, Issue 41 https://doi.org/10.1039/C4DT01935K	journal	January 2014
Defying strain in the synthesis of an electroactive bilayer helicene Milton, Margarita; Schuster, Nathaniel J.; Paley, Daniel W. Chemical Science, Vol. 10, Issue 4 https://doi.org/10.1039/C8SC04216K	journal	January 2019
Chiral intertwined spirals and magnetic transition dipole moments dictated by cylinder helicity Sato, Sota; Yoshii, Asami; Takahashi, Satsuki Proceedings of the National Academy of Sciences, Vol. 114, Issue 50 https://doi.org/10.1073/pnas.1717524114	journal	November 2017
Strong Enhancement of Nonlinear Optical Properties Through Supramolecular Chirality Verbiest, T. Science, Vol. 282, Issue 5390 https://doi.org/10.1126/science.282.5390.913	journal	October 1998
Synthesis of many different types of organic small molecules using one automated process Li, J.; Ballmer, S. G.; Gillis, E. P. Science, Vol. 347, Issue 6227 https://doi.org/10.1126/science.aaa5414	journal	March 2015

Similar Records

The Structural Origins of Intense Circular Dichroism in a Waggling Helicene Nanoribbon

Journal Article · Fri Apr 03 00:00:00 EDT 2020 · Journal of the American Chemical Society · OSTI ID:2202956

Defying strain in the synthesis of an electroactive bilayer helicene

Journal Article · Mon Nov 19 23:00:00 EST 2018 · Chemical Science · OSTI ID:1612238

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption
Chirality
Circular dichroism spectroscopy
Molecules
Optical properties

Chirality Amplified: Long, Discrete Helicene Nanoribbons

Citation Formats

References (52)

Linked Research (1)

Similar Records

Related Subjects