Arene Substitution Design for Controlled Conformational Changes of Dibenzocycloocta-1,5-dienes

Fu, Wenxin; Alam, Todd M.; Li, Jiachen; Bustamante, Jacqueline; Lien, Thanh; Adams, Ralph W.; Teat, Simon J.; Stokes, Benjamin J.; Yang, Weitao; Liu, Yi; Lu, Jennifer Q.

doi:10.1021/jacs.0c06579

Arene Substitution Design for Controlled Conformational Changes of Dibenzocycloocta-1,5-dienes

Journal Article · Thu Sep 03 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c06579· OSTI ID:1670754

Fu, Wenxin ^[1]; ^[2]; Li, Jiachen ^[3]; Bustamante, Jacqueline ^[1]; Lien, Thanh ^[1]; ^[4]; Teat, Simon J. ^[5]; ^[1]; ^[3]; ^[6]; Lu, Jennifer Q. ^[1]

Univ. of California, Merced, CA (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Duke Univ., Durham, NC (United States)
Univ. of Manchester (United Kingdom)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry

We report that the agile eight-mernbered cycloalkane can be stabilized by fusing two rigid benzene rings, substituted with proper functional groups. The conformational change of dibenzocycloocta-1,S-diene (DBCOD), a rigid-flexible-rigidorganic moiety, from Boat to Chair conformation requires an activation energy of 42 kJ/mol that is substantially lower than that of existing submolecular shape-changing unit. Experimental data corroborated by theory calculations demonstrate that intramolecular hydrogen bonding can stabilize Boat whereas electron repulsive interaction from opposing ester substituents favors Chair. Intramolecular hydrogen bonding, formed by 1,10-diamide substitution stabilizes Boat, spiking the temperature at which Boat and Chair can readily interchange from -60 °C to 60 °C. Concomitantly this intramolecular attraction raises the energy barrier from 42 kJ/mol of unsubstituted DBCOD to 68 kJ/mol of diamide-substituted DBCOD. Remarkably, this value falls within the range of the activation energy of highly efficient enzyme catalyzed biological reactions. With shape changes once considered only possible with high-energy, our work reveals a potential pathway exemplified by a specific submolecular structure to achieve low-energy driven shape changes for the first time. Together with intrinsic cycle stability and high energy output systems that would have incurred damage under high-energy stimuli, could particularly benefit from this new kind of low-energy driven shape-changing mechanism. This work has laid the basis to construct systems for low-energy driven stimuli-responsive applications, hitherto a challenge to overcome.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1670754

Alternate ID(s):: OSTI ID: 1777960

Report Number(s):: SAND--2020-8218J; 689825

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 39 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (63)

Direct Sun-Driven Artificial Heliotropism for Solar Energy Harvesting Based on a Photo-Thermomechanical Liquid-Crystal Elastomer Nanocomposite Li, Chensha; Liu, Ye; Huang, Xuezhen Advanced Functional Materials, Vol. 22, Issue 24 https://doi.org/10.1002/adfm.201202038	journal	August 2012
Three-Dimensional Photomobility of Crosslinked Azobenzene Liquid-Crystalline Polymer Fibers Yoshino, Taiki; Kondo, Mizuho; Mamiya, Jun-ichi Advanced Materials, Vol. 22, Issue 12 https://doi.org/10.1002/adma.200902879	journal	December 2009
A Near-Infrared Mechano Responsive Polymer System Uǧur, Gökçe; Chang, Jiyoung; Xiang, Shuhuai Advanced Materials, Vol. 24, Issue 20 https://doi.org/10.1002/adma.201104538	journal	April 2012
Quantitative IR Readout of Fulgimide Monolayer Switching on Si(111) Surfaces de Villeneuve, Catherine Henry; Michalik, Fabian; Chazalviel, Jean Noël Advanced Materials, Vol. 25, Issue 3 https://doi.org/10.1002/adma.201201546	journal	November 2012
Enlightening Materials with Photoswitches Goulet‐Hanssens, Alexis; Eisenreich, Fabian; Hecht, Stefan Advanced Materials, Vol. 32, Issue 20 https://doi.org/10.1002/adma.201905966	journal	January 2020
Reversible ON/OFF Nanoswitch for Organocatalysis: Mimicking the Locking and Unlocking Operation of CaMKII Schmittel, Michael; De, Soumen; Pramanik, Susnata Angewandte Chemie International Edition, Vol. 51, Issue 16 https://doi.org/10.1002/anie.201108089	journal	March 2012
Visible-Light-Triggered Molecular Photoswitch Based on Reversible E / Z Isomerization of a 1,2-Dicyanoethene Derivative Guo, Xin; Zhou, Jiawang; Siegler, Maxime A. Angewandte Chemie International Edition, Vol. 54, Issue 16 https://doi.org/10.1002/anie.201410945	journal	February 2015
High-Power Actuation from Molecular Photoswitches in Enantiomerically Paired Soft Springs Aßhoff, Sarah J.; Lancia, Federico; Iamsaard, Supitchaya Angewandte Chemie International Edition, Vol. 56, Issue 12 https://doi.org/10.1002/anie.201611325	journal	February 2017
Recent Implementations of Molecular Photoswitches into Smart Materials and Biological Systems Pianowski, Zbigniew L. Chemistry – A European Journal, Vol. 25, Issue 20 https://doi.org/10.1002/chem.201805814	journal	February 2019
Adjusting Local Molecular Environment for Giant Ambient Thermal Contraction Shen, Xingyuan; Connolly, Timothy; Huang, Yuhui Macromolecular Rapid Communications, Vol. 37, Issue 23 https://doi.org/10.1002/marc.201600045	journal	May 2016
Gas-phase conformations and exciton couplings in 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene Hamza, Abdulhamid Structural Chemistry, Vol. 21, Issue 4 https://doi.org/10.1007/s11224-010-9612-z	journal	April 2010
A Temperature-dependent Conformational Change in d-Amino Acid Oxidase and Its Effect on Catalysis Massey, Vincent; Curti, B.; Ganther, H. Journal of Biological Chemistry, Vol. 241, Issue 10 https://doi.org/10.1016/S0021-9258(18)96628-7	journal	May 1966
Design and Synthesis of Thermal Contracting Polymer with Unique Eight-Membered Carbocycle Unit Wang, Zhao; Huang, Yuhui; Guo, Jia Macromolecules, Vol. 51, Issue 4 https://doi.org/10.1021/acs.macromol.7b02705	journal	February 2018
Light-Driven DNA Nanomachine with a Photoresponsive Molecular Engine Kamiya, Yukiko; Asanuma, Hiroyuki Accounts of Chemical Research, Vol. 47, Issue 6 https://doi.org/10.1021/ar400308f	journal	March 2014
Photochromism of Diarylethene Molecules and Crystals: Memories, Switches, and Actuators Irie, Masahiro; Fukaminato, Tuyoshi; Matsuda, Kenji Chemical Reviews, Vol. 114, Issue 24 https://doi.org/10.1021/cr500249p	journal	November 2014
Diarylethenes for Memories and Switches Irie, Masahiro Chemical Reviews, Vol. 100, Issue 5 https://doi.org/10.1021/cr980069d	journal	May 2000
Fulgides for Memories and Switches Yokoyama, Yasushi Chemical Reviews, Vol. 100, Issue 5 https://doi.org/10.1021/cr980070c	journal	March 2000
Chiroptical Molecular Switches Feringa, Ben L.; van Delden, Richard A.; Koumura, Nagatoshi Chemical Reviews, Vol. 100, Issue 5 https://doi.org/10.1021/cr9900228	journal	May 2000
Isokinetic Relationship, Isoequilibrium Relationship, and Enthalpy−Entropy Compensation Liu, Lei; Guo, Qing-Xiang Chemical Reviews, Vol. 101, Issue 3 https://doi.org/10.1021/cr990416z	journal	March 2001
A study of the synthesis and properties of [26](1,2,3,4,5,6)cyclophane (superphane) Sekine, Yasuo; Boekelheide, V. Journal of the American Chemical Society, Vol. 103, Issue 7 https://doi.org/10.1021/ja00397a032	journal	April 1981
[2.2.2.2.2.2](1,2,3,4,5,6)Cyclophane: superphane Sekine, Y.; Brown, M.; Boekelheide, V. Journal of the American Chemical Society, Vol. 101, Issue 11 https://doi.org/10.1021/ja00505a053	journal	May 1979
Direct observation of chair and boat conformations for dibenzocycloocta-1,5-diene by nuclear magnetic resonance Montecalvo, Donald.; St. Jacques, Maurice.; Wasylishen, Rod. Journal of the American Chemical Society, Vol. 95, Issue 6 https://doi.org/10.1021/ja00787a057	journal	March 1973
Cis-trans isomerism in the pyridyl analogs of azobenzene. Kinetic and molecular orbital analysis Brown, Ellis V.; Granneman, G. Richard Journal of the American Chemical Society, Vol. 97, Issue 3 https://doi.org/10.1021/ja00836a025	journal	February 1975
Conformational Changes of 2,11-Dithia[3.3]metacyclophane. A New Look Using VT NMR and Calculation Mitchell, Reginald H. Journal of the American Chemical Society, Vol. 124, Issue 10 https://doi.org/10.1021/ja0173977	journal	March 2002
Thermally and Electrochemically Controllable Self-Complexing Molecular Switches Liu, Yi; Flood, Amar H.; Stoddart, J. Fraser Journal of the American Chemical Society, Vol. 126, Issue 30 https://doi.org/10.1021/ja048164t	journal	August 2004
Arylazopyrazoles: Azoheteroarene Photoswitches Offering Quantitative Isomerization and Long Thermal Half-Lives Weston, Claire E.; Richardson, Robert D.; Haycock, Peter R. Journal of the American Chemical Society, Vol. 136, Issue 34 https://doi.org/10.1021/ja505444d	journal	August 2014
Mechanism of OMP Decarboxylation in Orotidine 5′-Monophosphate Decarboxylase Hu, Hao; Boone, Amy; Yang, Weitao Journal of the American Chemical Society, Vol. 130, Issue 44 https://doi.org/10.1021/ja801202j	journal	October 2008
A pH Activated Configurational Rotary Switch: Controlling the E / Z Isomerization in Hydrazones Landge, Shainaz M.; Aprahamian, Ivan Journal of the American Chemical Society, Vol. 131, Issue 51 https://doi.org/10.1021/ja909149z	journal	December 2009
QM−FE and Molecular Dynamics Calculations on Catechol O -Methyltransferase: Free Energy of Activation in the Enzyme and in Aqueous Solution and Regioselectivity of the Enzyme-Catalyzed Reaction Kuhn, Bernd; Kollman, Peter A. Journal of the American Chemical Society, Vol. 122, Issue 11 https://doi.org/10.1021/ja992218v	journal	March 2000
Heterodiazocines: Synthesis and Photochromic Properties, Trans to Cis Switching within the Bio-optical Window Hammerich, Melanie; Schütt, Christian; Stähler, Cosima Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b05846	journal	September 2016
Near-Infrared Photoswitching of Azobenzenes under Physiological Conditions Dong, Mingxin; Babalhavaeji, Amirhossein; Collins, Catherine V. Journal of the American Chemical Society, Vol. 139, Issue 38 https://doi.org/10.1021/jacs.7b06471	journal	September 2017
Shape-Persistent Actuators from Hydrazone Photoswitches Ryabchun, Alexander; Li, Quan; Lancia, Federico Journal of the American Chemical Society, Vol. 141, Issue 3 https://doi.org/10.1021/jacs.8b11558	journal	January 2019
Taming the Complexity of Donor–Acceptor Stenhouse Adducts: Infrared Motion Pictures of the Complete Switching Pathway Zulfikri, Habiburrahman; Koenis, Mark A. J.; Lerch, Michael M. Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.9b00341	journal	April 2019
Selective oxidation of aldehydes to carboxylic acids with sodium chlorite-hydrogen peroxide Dalcanale, Enrico; Montanari, Fernando The Journal of Organic Chemistry, Vol. 51, Issue 4 https://doi.org/10.1021/jo00354a037	journal	February 1986
Conformation of Eight-Membered Benzoannulated Lactams by Combined NMR and DFT Studies Witosińska, Agnieszka; Musielak, Bogdan; Serda, Paweł The Journal of Organic Chemistry, Vol. 77, Issue 21 https://doi.org/10.1021/jo301859h	journal	October 2012
Theoretical Study of the Isomerization Mechanism of Azobenzene and Disubstituted Azobenzene Derivatives Crecca, Christina R.; Roitberg, Adrian E. The Journal of Physical Chemistry A, Vol. 110, Issue 26 https://doi.org/10.1021/jp057413c	journal	July 2006
Polarity Controlled Reaction Path and Kinetics of Thermal Cis-to-Trans Isomerization of 4-Aminoazobenzene Joshi, Neeraj Kumar; Fuyuki, Masanori; Wada, Akihide The Journal of Physical Chemistry B, Vol. 118, Issue 7 https://doi.org/10.1021/jp4125205	journal	February 2014
Quantum Chemical Investigation of Thermal Cis-to-Trans Isomerization of Azobenzene Derivatives: Substituent Effects, Solvent Effects, and Comparison to Experimental Data Dokić, Jadranka; Gothe, Marcel; Wirth, Jonas The Journal of Physical Chemistry A, Vol. 113, Issue 24 https://doi.org/10.1021/jp9021344	journal	May 2009
Optothermally Responsive Nanocomposite Generating Mechanical Forces for Cells Enabled by Few-Walled Carbon Nanotubes Zeng, Yuze; Lu, Jennifer Q. ACS Nano, Vol. 8, Issue 11 https://doi.org/10.1021/nn505042b	journal	October 2014
Phase Tag-Assisted Synthesis of Benzo[ b ]carbazole End-Capped Oligothiophenes Levick, Matthew T.; Coote, Susannah C.; Grace, Iain Organic Letters, Vol. 14, Issue 22 https://doi.org/10.1021/ol302748h	journal	October 2012
The Molecule Pages database Li, Joshua; Ning, Yuhong; Hedley, Warren Nature, Vol. 420, Issue 6916 https://doi.org/10.1038/nature01307	journal	December 2002
Large negative thermal expansion of a polymer driven by a submolecular conformational change Shen, Xingyuan; Viney, Christopher; Johnson, Erin R. Nature Chemistry, Vol. 5, Issue 12 https://doi.org/10.1038/nchem.1780	journal	October 2013
A chemically powered unidirectional rotary molecular motor based on a palladium redox cycle Collins, Beatrice S. L.; Kistemaker, Jos C. M.; Otten, Edwin Nature Chemistry, Vol. 8, Issue 9 https://doi.org/10.1038/nchem.2543	journal	June 2016
Stimuli-responsive nanocarriers for drug delivery Mura, Simona; Nicolas, Julien; Couvreur, Patrick Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3776	journal	October 2013
Programmable and adaptive mechanics with liquid crystal polymer networks and elastomers White, Timothy J.; Broer, Dirk J. Nature Materials, Vol. 14, Issue 11 https://doi.org/10.1038/nmat4433	journal	October 2015
Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend Leydecker, Tim; Herder, Martin; Pavlica, Egon Nature Nanotechnology, Vol. 11, Issue 9 https://doi.org/10.1038/nnano.2016.87	journal	June 2016
Role of outer surface probes for regulating ion gating of nanochannels Li, Xinchun; Zhai, Tianyou; Gao, Pengcheng Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-017-02447-7	journal	January 2018
Mechanical adaptability of artificial muscles from nanoscale molecular action Lancia, Federico; Ryabchun, Alexander; Nguindjel, Anne-Déborah Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12786-2	journal	October 2019
Optically switchable organic light-emitting transistors Hou, Lili; Zhang, Xiaoyan; Cotella, Giovanni F. Nature Nanotechnology, Vol. 14, Issue 4 https://doi.org/10.1038/s41565-019-0370-9	journal	February 2019
Photoisomerization in different classes of azobenzene Bandara, H. M. Dhammika; Burdette, Shawn C. Chem. Soc. Rev., Vol. 41, Issue 5 https://doi.org/10.1039/C1CS15179G	journal	January 2012
Spiropyran-based dynamic materials Klajn, Rafal Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60181A	journal	January 2014
The (photo)chemistry of Stenhouse photoswitches: guiding principles and system design Lerch, Michael M.; Szymański, Wiktor; Feringa, Ben L. Chemical Society Reviews, Vol. 47, Issue 6 https://doi.org/10.1039/C7CS00772H	journal	January 2018
Conformational behaviour of medium-sized rings. Part I. 5,6,11,12-Tetrahydrodibenzo[a,e]cyclo-octene (1,2,5,6-dibenzocyclo-octa-1,5-diene) and heterocyclic analogues Crossley, R.; Downing, A. P.; Nógrádi, M. J. Chem. Soc., Perkin Trans. 1, Issue 0 https://doi.org/10.1039/P19730000205	journal	January 1973
10. The action of sodium on o-xylylene dibromide Baker, Wilson; Banks, R.; Lyon, Donald R. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9450000027	journal	January 1945
The molecular structure of 6, 8, 6 and related systems Domiano, Paolo; Cozzini, Pietro; Claramunt, Rosa Mar�a Journal of the Chemical Society, Perkin Transactions 2, Issue 9 https://doi.org/10.1039/p29920001609	journal	January 1992
New molecular switch architectures Harris, Jared D.; Moran, Mark J.; Aprahamian, Ivan Proceedings of the National Academy of Sciences, Vol. 115, Issue 38 https://doi.org/10.1073/pnas.1714499115	journal	July 2018
Pneumatic artificial rubber muscle using shape-memory polymer sheet with embedded electrical heating wire Takashima, Kazuto; Sugitani, Kazuhiro; Morimoto, Naohiro Smart Materials and Structures, Vol. 23, Issue 12 https://doi.org/10.1088/0964-1726/23/12/125005	journal	October 2014
Shape memory polymer hexachiral auxetic structures with tunable stiffness Rossiter, Jonathan; Takashima, Kazuto; Scarpa, Fabrizio Smart Materials and Structures, Vol. 23, Issue 4 https://doi.org/10.1088/0964-1726/23/4/045007	journal	February 2014
A reversible single-molecule switch based on activated antiaromaticity Yin, Xiaodong; Zang, Yaping; Zhu, Liangliang Science Advances, Vol. 3, Issue 10 https://doi.org/10.1126/sciadv.aao2615	journal	October 2017
Stereodynamic Investigation of Dibenzo-1,5-cyclooctadiene and 5,6,11,12-tetrahydrodibenzo[ b , f ] [1,4]diazocine Derivatives Sauriol-Lord, Françoise; St-Jacques, Maurice Canadian Journal of Chemistry, Vol. 53, Issue 24 https://doi.org/10.1139/v75-545	journal	December 1975
Mechanisms Regulating the Reactions of Human Hemoglobin With Oxygen and Carbon Monoxide Perutz, Max F. Annual Review of Physiology, Vol. 52, Issue 1 https://doi.org/10.1146/annurev.ph.52.030190.000245	journal	October 1990
Thermal Cis -to- Trans Isomerization of Substituted Azobenzenes II. Substituent and Solvent Effects Nishimura, Norio; Sueyoshi, Toshinobu; Yamanaka, Hideyuki Bulletin of the Chemical Society of Japan, Vol. 49, Issue 5 https://doi.org/10.1246/bcsj.49.1381	journal	May 1976
The Thermal Isomerization of Azobenzenes. III. Substituent, Solvent, and Pressure Effects on the Thermal Isomerization of Push-pull Azobenzenes Nishimura, Norio; Kosako, Shinya; Sueishi, Yoshimi Bulletin of the Chemical Society of Japan, Vol. 57, Issue 6 https://doi.org/10.1246/bcsj.57.1617	journal	June 1984

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