ACS Publications. Most Trusted. Most Cited. Most Read

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2020, 142, 1, 606-613
RETURN TO ISSUEPREVArticleNEXT

Oriented Internal Electrostatic Fields Cooperatively Promote Ground- and Excited-State Reactivity: A Case Study in Photochemical CO2 Capture

  • Mitchell T. Blyth
    Mitchell T. Blyth
    ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia
    More by Mitchell T. Blyth
    Orcidhttp://orcid.org/0000-0001-9371-6515
  • , 
  • Benjamin B. Noble
    Benjamin B. Noble
    ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia
    More by Benjamin B. Noble
  • , 
  • Isabella C. Russell
    Isabella C. Russell
    ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia
    More by Isabella C. Russell
  • , and 
  • Michelle L. Coote*
    Michelle L. Coote
    ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 2601, Australia
    *[email protected]
    More by Michelle L. Coote
    Orcidhttp://orcid.org/0000-0003-0828-7053
Cite this: J. Am. Chem. Soc. 2020, 142, 1, 606–613
Publication Date (Web):December 12, 2019
https://doi.org/10.1021/jacs.9b12186
Copyright © 2019 American Chemical Society
Request reuse permissions

    Article Views

    3606

    Altmetric

    -

    Citations

    41
    LEARN ABOUT THESE METRICS
    Read OnlinePDF (2 MB)
    Get e-Alerts
    Supporting Info (1)»
    SUBJECTS:

    Abstract

    Abstract Image

    Oriented electrostatic fields can exert catalytic effects upon both the kinetics and the thermodynamics of chemical reactions; however, the vast majority of studies thus far have focused upon ground-state chemistry and rarely consider any more than a single class of reaction. In the present study, we first use density functional theory (DFT) calculations to clarify the mechanism of CO2 storage via photochemical carboxylation of o-alkylphenyl ketones, originally proposed by Murakami et al. (J. Am. Chem. Soc.2015, 137, 14063); we then demonstrate that oriented internal electrostatic fields arising from remote charged functional groups (CFGs) can selectively and cooperatively promote both ground- and excited-state chemical reactivity at all points along the revised mechanism, in a manner otherwise difficult to access via classical substituent effects. What is particularly striking is that electrostatic field effects upon key photochemical transitions are predictably enhanced in increasingly polar solvents, thus overcoming a central limitation of the electrostatic catalysis paradigm. We explain these observations, which should be readily extendable to the ground state.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.9b12186.

    • All computational data, additional data analysis and summaries, and data accompanying figures; electronic energies and Gibbs free energy and components, solvent corrections, imaginary frequencies, IRC coordinate scans, point charge approximations, σ-induction controls, excited-state dipole and polarizability analysis, comparison to classical substituent effects, conical intersection data; and Gaussian archives for all reported species (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 41 publications.

    1. Chenghui Zhu, Le Nhan Pham, Xu Yuan, Haoran Ouyang, Michelle L. Coote, Xinxing Zhang. High Electric Fields on Water Microdroplets Catalyze Spontaneous and Fast Reactions in Halogen-Bond Complexes. Journal of the American Chemical Society 2023, Article ASAP.
    2. Oisin J. Shiels, Samuel J. P. Marlton, Adam J. Trevitt. Protonation Isomer Specific Ion–Molecule Radical Reactions. Journal of the American Chemical Society 2023, 145 (28) , 15024-15029. https://doi.org/10.1021/jacs.3c02552
    3. Kshatresh Dutta Dubey, Thijs Stuyver, Sason Shaik. Local Electric Fields: From Enzyme Catalysis to Synthetic Catalyst Design. The Journal of Physical Chemistry B 2022, 126 (49) , 10285-10294. https://doi.org/10.1021/acs.jpcb.2c06422
    4. Guanheng Huang, Chen Zhou, Runhui Liang, Shanshan Sun, Ziqi Deng, Jiayu Li, Li Dang, David Lee Phillips, Ming-De Li. Ultrafast Time-Resolved Spectroscopic Study on the Photophysical and Photochemical Reaction Mechanisms of ortho-Methylbenzophenone in Selected Solutions. The Journal of Physical Chemistry B 2022, 126 (45) , 9388-9398. https://doi.org/10.1021/acs.jpcb.2c06452
    5. Jiao Yu J. Wang, Mitchell T. Blyth, Michael S. Sherburn, Michelle L. Coote. Tuning Photoenolization-Driven Cycloadditions Using Theory and Spectroscopy. Journal of the American Chemical Society 2022, 144 (2) , 1023-1033. https://doi.org/10.1021/jacs.1c12174
    6. Xin Xu, Shengheng Yan, Xiaodong Hou, Wei Song, Lei Wang, Tianfu Wu, Mengya Qi, Jing Wu, Yijian Rao, Binju Wang, Liming Liu. Local Electric Field Modulated Reactivity of Pseudomonas aeruginosa Acid Phosphatase for Enhancing Phosphorylation of l-Ascorbic Acid. ACS Catalysis 2021, 11 (21) , 13397-13407. https://doi.org/10.1021/acscatal.1c04200
    7. Irma Avdic, Emily M. Kempfer-Robertson, Lee M. Thompson. Oriented External Electric Field Tuning of Unsubstituted Azoheteroarene Thermal Isomerization Half-Lives. The Journal of Physical Chemistry A 2021, 125 (37) , 8238-8248. https://doi.org/10.1021/acs.jpca.1c06102
    8. Li-Juan Yu, Michelle L. Coote. Electrostatic Switching of Stereoselectivity in Aldol Reactions. The Journal of Organic Chemistry 2021, 86 (13) , 9076-9083. https://doi.org/10.1021/acs.joc.1c01032
    9. Patrick A. Robertson, Hannah M. Bishop, Andrew J. Orr-Ewing. Tuning the Excited-State Dynamics of Acetophenone Using Metal Ions in Solution. The Journal of Physical Chemistry Letters 2021, 12 (23) , 5473-5478. https://doi.org/10.1021/acs.jpclett.1c01466
    10. Ruibin Liang, Jimmy K. Yu, Jan Meisner, Fang Liu, Todd J. Martinez. Electrostatic Control of Photoisomerization in Channelrhodopsin 2. Journal of the American Chemical Society 2021, 143 (14) , 5425-5437. https://doi.org/10.1021/jacs.1c00058
    11. Roey Sagi, Michelle Akerman, Sujith Ramakrishnan, Micha Asscher. Solid Ammonia Charging by Low-Energy Electrons. The Journal of Physical Chemistry C 2021, 125 (7) , 3845-3858. https://doi.org/10.1021/acs.jpcc.0c09658
    12. Samuel J. P. Marlton, Benjamin I. McKinnon, Nicholas S. Hill, Michelle L. Coote, Adam J. Trevitt. Electrostatically Tuning the Photodissociation of the Irgacure 2959 Photoinitiator in the Gas Phase by Cation Binding. Journal of the American Chemical Society 2021, 143 (5) , 2331-2339. https://doi.org/10.1021/jacs.0c11978
    13. Christopher Panaritis, Yasmine M. Hajar, Laureline Treps, Carine Michel, Elena A. Baranova, Stephan N. Steinmann. Demystifying the Atomistic Origin of the Electric Field Effect on Methane Oxidation. The Journal of Physical Chemistry Letters 2020, 11 (17) , 6976-6981. https://doi.org/10.1021/acs.jpclett.0c01485
    14. Vincent Doan, Benjamin B. Noble, Michelle L. Coote. Electrostatic Activation of Tetrazoles. The Journal of Organic Chemistry 2020, 85 (15) , 10091-10097. https://doi.org/10.1021/acs.joc.0c01354
    15. Sason Shaik, David Danovich, Jyothish Joy, Zhanfeng Wang, Thijs Stuyver. Electric-Field Mediated Chemistry: Uncovering and Exploiting the Potential of (Oriented) Electric Fields to Exert Chemical Catalysis and Reaction Control. Journal of the American Chemical Society 2020, 142 (29) , 12551-12562. https://doi.org/10.1021/jacs.0c05128
    16. Longkun Xu, Ekaterina I. Izgorodina, Michelle L. Coote. Ordered Solvents and Ionic Liquids Can Be Harnessed for Electrostatic Catalysis. Journal of the American Chemical Society 2020, 142 (29) , 12826-12833. https://doi.org/10.1021/jacs.0c05643
    17. Samuel J. P. Marlton, Benjamin I. McKinnon, Boris Ucur, James P. Bezzina, Stephen J. Blanksby, Adam J. Trevitt. Discrimination between Protonation Isomers of Quinazoline by Ion Mobility and UV-Photodissociation Action Spectroscopy. The Journal of Physical Chemistry Letters 2020, 11 (10) , 4226-4231. https://doi.org/10.1021/acs.jpclett.0c01009
    18. Karthik Gopakumar, Sason Shaik, Rajeev Ramanan. Two‐Way Catalysis in a Diels–Alder Reaction Limits Inhibition Induced by an External Electric Field. Angewandte Chemie 2023, 135 (38) https://doi.org/10.1002/ange.202307579
    19. Karthik Gopakumar, Sason Shaik, Rajeev Ramanan. Two‐Way Catalysis in a Diels–Alder Reaction Limits Inhibition Induced by an External Electric Field. Angewandte Chemie International Edition 2023, 62 (38) https://doi.org/10.1002/anie.202307579
    20. Ankur K. Guha. Oriented electric field stabilized beryllium dimer. International Journal of Quantum Chemistry 2023, 123 (16) https://doi.org/10.1002/qua.27138
    21. Navya Arepalli, Sukanta Mondal, Debdutta Chakraborty, Pratim Kumar Chattaraj. Impact of Static-Oriented Electric Fields on the Kinetics of Some Representative Suzuki–Miyaura and Metal-Cluster Mediated Reactions. Molecules 2023, 28 (16) , 6169. https://doi.org/10.3390/molecules28166169
    22. Fu-De Ren, Ying-Zhe Liu, Xiao-Lei Wang, Li-Li Qiu, Zi-Hui Meng, Xiang Cheng, Yong-Xiang Li. Strong External Electric Fields Reduce Explosive Sensitivity: A Theoretical Investigation into the Reaction Selectivity in NH2NO2∙∙∙NH3. Molecules 2023, 28 (6) , 2586. https://doi.org/10.3390/molecules28062586
    23. Emily M. Kempfer-Robertson, Irma Avdic, Meagan N. Haase, Thomas Dane Pike, Lee M. Thompson. Protonation state control of electric field induced molecular switching mechanisms. Physical Chemistry Chemical Physics 2023, 25 (6) , 5251-5261. https://doi.org/10.1039/D2CP04494C
    24. Efstratios M. Kritikos, Aditya Lele, Adri C. T. van Duin, Andrea Giusti. Atomistic insight into the effects of electrostatic fields on hydrocarbon reaction kinetics. The Journal of Chemical Physics 2023, 158 (5) https://doi.org/10.1063/5.0134785
    25. Meng Li, Xinjie Wan, Xin He, Chunying Rong, Shubin Liu. Impacts of external fields on aromaticity and acidity of benzoic acid: a density functional theory, conceptual density functional theory and information-theoretic approach study. Physical Chemistry Chemical Physics 2023, 25 (3) , 2595-2605. https://doi.org/10.1039/D2CP04557E
    26. Jiami Guo, Zi-An Shen, Xueting Zhou, Lei Dai, Yixin Lu. Light-induced phosphine-catalyzed asymmetric functionalization of benzylic C-H bonds. Science China Chemistry 2023, 66 (1) , 127-132. https://doi.org/10.1007/s11426-022-1406-y
    27. Mitchell T. Blyth, Michelle L. Coote. Manipulation of N-heterocyclic carbene reactivity with practical oriented electric fields. Physical Chemistry Chemical Physics 2022, 25 (1) , 375-383. https://doi.org/10.1039/D2CP04507A
    28. Xin‐Long Hu, Yuan‐Xu Jiang, Lei Song, Da‐Gang Yu. CH Carboxylation with CO 2. 2022, 1-20. https://doi.org/10.1002/9783527834242.chf0171
    29. Alexander B. Weberg, Ryan P. Murphy, Neil C. Tomson. Oriented internal electrostatic fields: an emerging design element in coordination chemistry and catalysis. Chemical Science 2022, 13 (19) , 5432-5446. https://doi.org/10.1039/D2SC01715F
    30. Margaret L. Kelty, Andrew J. McNeece, Josh W. Kurutz, Alexander S. Filatov, John S. Anderson. Electrostatic vs. inductive effects in phosphine ligand donor properties and reactivity. Chemical Science 2022, 13 (15) , 4377-4387. https://doi.org/10.1039/D1SC04277G
    31. Dongliang Hu, Xingyu Gu, Lei Lyu, Jianzhong Pei, Bingyan Cui. Investigating the aging mechanism of asphaltene and its dependence on environmental factors through AIMD simulations and DFT calculations. Science of The Total Environment 2021, 795 , 148897. https://doi.org/10.1016/j.scitotenv.2021.148897
    32. Leizhi Zheng, Guoqiang Yang, Xingbang Hu, Zhibing Zhang. CO2 capturing and in situ conversion at mild condition: Efficient synthesis of methyl phenyl carbonate. Journal of Environmental Chemical Engineering 2021, 9 (5) , 105862. https://doi.org/10.1016/j.jece.2021.105862
    33. Zheyuan Xu, Deguang Liu, Haizhu Yu, Mårten S.G. Ahlquist, Yao Fu. Mechanistic study on the photo carboxylation of benzylic C-H bonds by xanthone and Ni(0) catalysts. Molecular Catalysis 2021, 514 , 111785. https://doi.org/10.1016/j.mcat.2021.111785
    34. Alexander B. Weberg, Samuel P. McCollom, Laura M. Thierer, Michael R. Gau, Patrick J. Carroll, Neil C. Tomson. Using internal electrostatic fields to manipulate the valence manifolds of copper complexes. Chemical Science 2021, 12 (12) , 4395-4404. https://doi.org/10.1039/D0SC06364A
    35. Guodong Zhang, Yihan Cheng, Matthias Beller, Feng Chen. Direct Carboxylation with Carbon Dioxide via Cooperative Photoredox and Transition‐Metal Dual Catalysis. Advanced Synthesis & Catalysis 2021, 363 (6) , 1583-1596. https://doi.org/10.1002/adsc.202001280
    36. Fu-de Ren, Wen-jing Shi, Duan-lin Cao, Yong-xiang Li, De-hua Zhang, Xian-feng Wang, Zhao-yang Shi. External electric field reduces the explosive sensitivity: a theoretical investigation into the hydrogen transference kinetics of the NH2NO2∙∙∙H2O complex. Journal of Molecular Modeling 2020, 26 (12) https://doi.org/10.1007/s00894-020-04607-x
    37. Jie Chen, Siyuan Liu, Meng Li, Chunying Rong, Shubin Liu. A density functional theory and information-theoretic approach study of chiral molecules in external electric fields. Chemical Physics Letters 2020, 757 , 137858. https://doi.org/10.1016/j.cplett.2020.137858
    38. Yanbin Zhang, Ruiwen Jin, Guangxing Pan, Hao Guo. Light-enabled, AlCl 3 -catalyzed regioselective intramolecular nucleophilic addition of non-nucleophilic alkyls to alkynes. Chemical Communications 2020, 56 (78) , 11621-11624. https://doi.org/10.1039/D0CC04636A
    39. Bangaru Bhaskararao, Dong Yeon Kim, Jenica Marie L. Madridejos, Cheol-Min Park, Kwang S. Kim. Rational design of metal–ligands for the conversion of CH 4 and CO 2 to acetates: role of acids and Lewis acids. Journal of Materials Chemistry A 2020, 8 (29) , 14671-14679. https://doi.org/10.1039/D0TA04002A
    40. Wei-Wei Wang, Chang-Wei Wang, Jia-Jia Zheng, Fu-Lin Shang, Jing-Shuang Dang, Xiang Zhao. Directional Diels–Alder cycloadditions of isoelectronic graphene and hexagonal boron nitride in oriented external electric fields: reaction axis rule vs. polarization axis rule. Nanoscale 2020, 12 (28) , 15364-15370. https://doi.org/10.1039/D0NR03443F
    41. Keyi Tian, Ruonan Chen, Jiafang Xu, Ge Yang, Xintong Xu, Yanhua Zhang. Understanding the Photo- and Electro-Carboxylation of o-Methylbenzophenone with Carbon Dioxide. Catalysts 2020, 10 (6) , 664. https://doi.org/10.3390/catal10060664
    Download PDF

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect