{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T15:07:51Z","timestamp":1790003271809,"version":"4.0.1"},"reference-count":53,"publisher":"Wiley","issue":"39","license":[{"start":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T00:00:00Z","timestamp":1785110400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T00:00:00Z","timestamp":1785110400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,9,21]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The influence of local electrostatic environments on catalytic reactivity is well established in enzymatic systems, but their systematic implementation in synthetic catalysts remains limited. Here, we investigate the dynamic binding of alkali\u2010metal cations to a cobalt porphyrin cage complex as a strategy to modulate its redox properties and catalytic activity toward CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction (CO\n                    <jats:sub>2<\/jats:sub>\n                    RR). Electrochemical studies reveal that the Co\n                    <jats:sup>1<\/jats:sup>\n                    <jats:sup>+<\/jats:sup>\n                    \u00a0\u2192\u00a0Co\n                    <jats:sup>0<\/jats:sup>\n                    redox potential is highly sensitive to the identity of the electrolyte cation, with K\n                    <jats:sup>+<\/jats:sup>\n                    and Cs\n                    <jats:sup>+<\/jats:sup>\n                    inducing the largest positive shifts (236 and 225\u00a0mV, respectively), resulting in substantial decreases in CO\n                    <jats:sub>2<\/jats:sub>\n                    RR overpotential. In contrast, Li\n                    <jats:sup>+<\/jats:sup>\n                    , Na\n                    <jats:sup>+<\/jats:sup>\n                    , and Ca\n                    <jats:sup>2<\/jats:sup>\n                    <jats:sup>+<\/jats:sup>\n                    produce only minor or moderate effects. Molecular dynamics simulations rationalize these observations in terms of binding mode and dynamics: Li\n                    <jats:sup>+<\/jats:sup>\n                    remains fully solvated, Na\n                    <jats:sup>+<\/jats:sup>\n                    interacts weakly with the cage, while K\n                    <jats:sup>+<\/jats:sup>\n                    and Cs\n                    <jats:sup>+<\/jats:sup>\n                    bind specifically and symmetrically to the ether\u2010functionalized cage walls, with oxidation\u2010state\u2010dependent occupancy. These findings illustrate how alkali\u2010metal ion coordination can be harnessed to modulate molecular electrocatalysts and guide the design of redox\u2010tunable systems.\n                  <\/jats:p>","DOI":"10.1002\/anie.9925316","type":"journal-article","created":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T12:12:47Z","timestamp":1785154367000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Dynamic Binding of Alkali\u2010Metal Ions in a Metalloporphyrin Cage: Impact on Redox Catalysis"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4167-4891","authenticated-orcid":false,"given":"Eva","family":"Pluha\u0159ov\u00e1","sequence":"first","affiliation":[{"name":"J. Heyrovsk\u00fd Institute of Physical Chemistry v.v.i. The Czech Academy of Sciences  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Adarsh Koovakattil","family":"Surendran","sequence":"additional","affiliation":[{"name":"Institute for Molecules and Materials Radboud University  Nijmegen The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Karol\u00edna","family":"F\u00e1rn\u00edkov\u00e1","sequence":"additional","affiliation":[{"name":"J. Heyrovsk\u00fd Institute of Physical Chemistry v.v.i. The Czech Academy of Sciences  Prague Czech Republic"},{"name":"University of Chemistry and Technology Prague  Prague Czech Republic"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jana","family":"Roithov\u00e1","sequence":"additional","affiliation":[{"name":"Institute for Molecules and Materials Radboud University  Nijmegen The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Evert Jan","family":"Meijer","sequence":"additional","affiliation":[{"name":"Van \u2019t Hoff Institute for Molecular Sciences and Amsterdam Center for Multiscale Modelling University of Amsterdam  Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,7,27]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c05128"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b01701"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2SC01715F"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021\u20109258(18)35647\u20103"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1147753"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr950045w"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.3c00536"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c02084"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1148597"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja301685r"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41586\u2010020\u20102137\u20108"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.0c02073"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.5c00759"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201803873"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b12404"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201802585"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202209396"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c06121"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.4c00487"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.abd2569"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2023.09.023"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.2122677119"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacsau.4c00213"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/ntls.20220019"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0700554104"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja106197e"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201300098"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b07014"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.2c00080"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c03501"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9EE01341E"},{"key":"e_1_2_9_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b06765"},{"key":"e_1_2_9_34_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.theochem.2009.10.025"},{"key":"e_1_2_9_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp0622637"},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CP01957G"},{"key":"e_1_2_9_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2019.07.009"},{"key":"e_1_2_9_38_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.softx.2015.06.001"},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21287"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ci300363c"},{"key":"e_1_2_9_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.7b01236"},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemphys.2003.08.006"},{"key":"e_1_2_9_43_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268976.2019.1650209"},{"key":"e_1_2_9_44_1","unstructured":"M. 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