---
_id: '14664'
abstract:
- lang: eng
  text: The architecture of self-assembled host molecules can profoundly affect the
    properties of the encapsulated guests. For example, a rigid cage with small windows
    can efficiently protect its contents from the environment; in contrast, tube-shaped,
    flexible hosts with large openings and an easily accessible cavity are ideally
    suited for catalysis. Here, we report a “Janus” nature of a Pd6L4 coordination
    host previously reported to exist exclusively as a tube isomer (T). We show that
    upon encapsulating various tetrahedrally shaped guests, T can reconfigure into
    a cage-shaped host (C) in quantitative yield. Extracting the guest affords empty
    C, which is metastable and spontaneously relaxes to T, and the T⇄C interconversion
    can be repeated for multiple cycles. Reversible toggling between two vastly different
    isomers paves the way toward controlling functional properties of coordination
    hosts “on demand”.
acknowledgement: We acknowledge funding from the European Union’s Horizon 2020 Research
  and Innovation Program under the European Research Council (grant agreement 820008).We
  also thank the Deutsche Forschungsgemeinschaft (DFG) for support through priority
  program SPP1807(CL489/3-2) and RESOLV Cluster of Excellence EXC2033 (project number
  390677874). A.B.G. acknowledges funding from the Zuckerman STEM Leadership Program.
  DFT calculations were carried out using resources provided by the Wrocław Center
  for Networking and Supercomputing, grant 329.
article_processing_charge: Yes (in subscription journal)
article_type: original
author:
- first_name: Kuntrapakam
  full_name: Hema, Kuntrapakam
  last_name: Hema
- first_name: Angela B.
  full_name: Grommet, Angela B.
  last_name: Grommet
- first_name: Michał J.
  full_name: Białek, Michał J.
  last_name: Białek
- first_name: Jinhua
  full_name: Wang, Jinhua
  last_name: Wang
- first_name: Laura
  full_name: Schneider, Laura
  last_name: Schneider
- first_name: Christoph
  full_name: Drechsler, Christoph
  last_name: Drechsler
- first_name: Oksana
  full_name: Yanshyna, Oksana
  last_name: Yanshyna
- first_name: Yael
  full_name: Diskin-Posner, Yael
  last_name: Diskin-Posner
- first_name: Guido H.
  full_name: Clever, Guido H.
  last_name: Clever
- first_name: Rafal
  full_name: Klajn, Rafal
  id: 8e84690e-1e48-11ed-a02b-a1e6fb8bb53b
  last_name: Klajn
citation:
  ama: Hema K, Grommet AB, Białek MJ, et al. Guest encapsulation alters the thermodynamic
    landscape of a coordination host. <i>Journal of the American Chemical Society</i>.
    2023;145(45):24755-24764. doi:<a href="https://doi.org/10.1021/jacs.3c08666">10.1021/jacs.3c08666</a>
  apa: Hema, K., Grommet, A. B., Białek, M. J., Wang, J., Schneider, L., Drechsler,
    C., … Klajn, R. (2023). Guest encapsulation alters the thermodynamic landscape
    of a coordination host. <i>Journal of the American Chemical Society</i>. American
    Chemical Society. <a href="https://doi.org/10.1021/jacs.3c08666">https://doi.org/10.1021/jacs.3c08666</a>
  chicago: Hema, Kuntrapakam, Angela B. Grommet, Michał J. Białek, Jinhua Wang, Laura
    Schneider, Christoph Drechsler, Oksana Yanshyna, Yael Diskin-Posner, Guido H.
    Clever, and Rafal Klajn. “Guest Encapsulation Alters the Thermodynamic Landscape
    of a Coordination Host.” <i>Journal of the American Chemical Society</i>. American
    Chemical Society, 2023. <a href="https://doi.org/10.1021/jacs.3c08666">https://doi.org/10.1021/jacs.3c08666</a>.
  ieee: K. Hema <i>et al.</i>, “Guest encapsulation alters the thermodynamic landscape
    of a coordination host,” <i>Journal of the American Chemical Society</i>, vol.
    145, no. 45. American Chemical Society, pp. 24755–24764, 2023.
  ista: Hema K, Grommet AB, Białek MJ, Wang J, Schneider L, Drechsler C, Yanshyna
    O, Diskin-Posner Y, Clever GH, Klajn R. 2023. Guest encapsulation alters the thermodynamic
    landscape of a coordination host. Journal of the American Chemical Society. 145(45),
    24755–24764.
  mla: Hema, Kuntrapakam, et al. “Guest Encapsulation Alters the Thermodynamic Landscape
    of a Coordination Host.” <i>Journal of the American Chemical Society</i>, vol.
    145, no. 45, American Chemical Society, 2023, pp. 24755–64, doi:<a href="https://doi.org/10.1021/jacs.3c08666">10.1021/jacs.3c08666</a>.
  short: K. Hema, A.B. Grommet, M.J. Białek, J. Wang, L. Schneider, C. Drechsler,
    O. Yanshyna, Y. Diskin-Posner, G.H. Clever, R. Klajn, Journal of the American
    Chemical Society 145 (2023) 24755–24764.
date_created: 2023-12-10T23:00:59Z
date_published: 2023-11-02T00:00:00Z
date_updated: 2023-12-11T11:47:07Z
day: '02'
ddc:
- '540'
department:
- _id: RaKl
doi: 10.1021/jacs.3c08666
external_id:
  pmid:
  - '37917939'
file:
- access_level: open_access
  checksum: a1f37df6b83f88f51ba64468ce0c1589
  content_type: application/pdf
  creator: dernst
  date_created: 2023-12-11T11:44:54Z
  date_updated: 2023-12-11T11:44:54Z
  file_id: '14675'
  file_name: 2023_JACS_Hema.pdf
  file_size: 4304472
  relation: main_file
  success: 1
file_date_updated: 2023-12-11T11:44:54Z
has_accepted_license: '1'
intvolume: '       145'
issue: '45'
language:
- iso: eng
month: '11'
oa: 1
oa_version: Published Version
page: 24755-24764
pmid: 1
publication: Journal of the American Chemical Society
publication_identifier:
  eissn:
  - 1520-5126
  issn:
  - 0002-7863
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Guest encapsulation alters the thermodynamic landscape of a coordination host
tmp:
  image: /images/cc_by.png
  legal_code_url: https://creativecommons.org/licenses/by/4.0/legalcode
  name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
  short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 145
year: '2023'
...
---
_id: '13340'
abstract:
- lang: eng
  text: Photoisomerization of azobenzenes from their stable E isomer to the metastable
    Z state is the basis of numerous applications of these molecules. However, this
    reaction typically requires ultraviolet light, which limits applicability. In
    this study, we introduce disequilibration by sensitization under confinement (DESC),
    a supramolecular approach to induce the E-to-Z isomerization by using light of
    a desired color, including red. DESC relies on a combination of a macrocyclic
    host and a photosensitizer, which act together to selectively bind and sensitize
    E-azobenzenes for isomerization. The Z isomer lacks strong affinity for and is
    expelled from the host, which can then convert additional E-azobenzenes to the
    Z state. In this way, the host–photosensitizer complex converts photon energy
    into chemical energy in the form of out-of-equilibrium photostationary states,
    including ones that cannot be accessed through direct photoexcitation.
acknowledgement: We acknowledge funding from the European Union’s Horizon 2020 Research
  and Innovation Program [European Research Council grants 820008 (Ra.K.) and 101045223
  (A.P.) and Marie Skłodowska-Curie grants 812868 (J.G.) and 101022777 (T.-P.R.)],
  the Academy of Finland [Center of Excellence Programme LIBER grant 346107 (A.P.),
  Flagship Programme PREIN grant 320165 (A.P.), and Postdoctoral Researcher grant
  340103 (T.-P.R.)], Zuckerman STEM Leadership Program Fellowship (J.R.C.), President’s
  PhD Scholarship (M.O.), and the EPSRC [Established Career Fellowship grant EP/R00188X/1
  (M.J.F.)].
article_processing_charge: No
article_type: original
author:
- first_name: Julius
  full_name: Gemen, Julius
  last_name: Gemen
- first_name: Jonathan R.
  full_name: Church, Jonathan R.
  last_name: Church
- first_name: Tero-Petri
  full_name: Ruoko, Tero-Petri
  last_name: Ruoko
- first_name: Nikita
  full_name: Durandin, Nikita
  last_name: Durandin
- first_name: Michał J.
  full_name: Białek, Michał J.
  last_name: Białek
- first_name: Maren
  full_name: Weissenfels, Maren
  last_name: Weissenfels
- first_name: Moran
  full_name: Feller, Moran
  last_name: Feller
- first_name: Miri
  full_name: Kazes, Miri
  last_name: Kazes
- first_name: Veniamin A.
  full_name: Borin, Veniamin A.
  last_name: Borin
- first_name: Magdalena
  full_name: Odaybat, Magdalena
  last_name: Odaybat
- first_name: Rishir
  full_name: Kalepu, Rishir
  last_name: Kalepu
- first_name: Yael
  full_name: Diskin-Posner, Yael
  last_name: Diskin-Posner
- first_name: Dan
  full_name: Oron, Dan
  last_name: Oron
- first_name: Matthew J.
  full_name: Fuchter, Matthew J.
  last_name: Fuchter
- first_name: Arri
  full_name: Priimagi, Arri
  last_name: Priimagi
- first_name: Igor
  full_name: Schapiro, Igor
  last_name: Schapiro
- first_name: Rafal
  full_name: Klajn, Rafal
  id: 8e84690e-1e48-11ed-a02b-a1e6fb8bb53b
  last_name: Klajn
citation:
  ama: Gemen J, Church JR, Ruoko T-P, et al. Disequilibrating azoarenes by visible-light
    sensitization under confinement. <i>Science</i>. 2023;381(6664):1357-1363. doi:<a
    href="https://doi.org/10.1126/science.adh9059">10.1126/science.adh9059</a>
  apa: Gemen, J., Church, J. R., Ruoko, T.-P., Durandin, N., Białek, M. J., Weissenfels,
    M., … Klajn, R. (2023). Disequilibrating azoarenes by visible-light sensitization
    under confinement. <i>Science</i>. American Association for the Advancement of
    Science. <a href="https://doi.org/10.1126/science.adh9059">https://doi.org/10.1126/science.adh9059</a>
  chicago: Gemen, Julius, Jonathan R. Church, Tero-Petri Ruoko, Nikita Durandin, Michał
    J. Białek, Maren Weissenfels, Moran Feller, et al. “Disequilibrating Azoarenes
    by Visible-Light Sensitization under Confinement.” <i>Science</i>. American Association
    for the Advancement of Science, 2023. <a href="https://doi.org/10.1126/science.adh9059">https://doi.org/10.1126/science.adh9059</a>.
  ieee: J. Gemen <i>et al.</i>, “Disequilibrating azoarenes by visible-light sensitization
    under confinement,” <i>Science</i>, vol. 381, no. 6664. American Association for
    the Advancement of Science, pp. 1357–1363, 2023.
  ista: Gemen J, Church JR, Ruoko T-P, Durandin N, Białek MJ, Weissenfels M, Feller
    M, Kazes M, Borin VA, Odaybat M, Kalepu R, Diskin-Posner Y, Oron D, Fuchter MJ,
    Priimagi A, Schapiro I, Klajn R. 2023. Disequilibrating azoarenes by visible-light
    sensitization under confinement. Science. 381(6664), 1357–1363.
  mla: Gemen, Julius, et al. “Disequilibrating Azoarenes by Visible-Light Sensitization
    under Confinement.” <i>Science</i>, vol. 381, no. 6664, American Association for
    the Advancement of Science, 2023, pp. 1357–63, doi:<a href="https://doi.org/10.1126/science.adh9059">10.1126/science.adh9059</a>.
  short: J. Gemen, J.R. Church, T.-P. Ruoko, N. Durandin, M.J. Białek, M. Weissenfels,
    M. Feller, M. Kazes, V.A. Borin, M. Odaybat, R. Kalepu, Y. Diskin-Posner, D. Oron,
    M.J. Fuchter, A. Priimagi, I. Schapiro, R. Klajn, Science 381 (2023) 1357–1363.
date_created: 2023-08-01T08:26:15Z
date_published: 2023-09-22T00:00:00Z
date_updated: 2023-10-03T08:11:26Z
day: '22'
department:
- _id: RaKl
doi: 10.1126/science.adh9059
intvolume: '       381'
issue: '6664'
language:
- iso: eng
main_file_link:
- open_access: '1'
  url: https://doi.org/10.26434/chemrxiv-2023-gq2h0
month: '09'
oa: 1
oa_version: Preprint
page: 1357-1363
publication: Science
publication_identifier:
  eissn:
  - 1095-9203
publication_status: published
publisher: American Association for the Advancement of Science
quality_controlled: '1'
scopus_import: '1'
status: public
title: Disequilibrating azoarenes by visible-light sensitization under confinement
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 381
year: '2023'
...