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To shed light on this at the molecular level, the response to a static field was computationally investigated for two structurally related MOFs, depending on their loading with guest molecules. The pillared-layer MOFs differ in their pillar moiety, with one bearing a rotatable permanent dipole moment and the other being non-polar. Two guest molecules with and without polarity, namely, methanol and methane, were considered. A comprehensive picture of the response of the guest molecules could be achieved with respect to both the amount and polarity of the confined species. For both MOFs, the dielectric response is very sensitive to the introduction of methanol, showing an anisotropic and non-linear increase in the system\u2019s relative permittivity expressed by a strongly increasing polarization response to external electric fields scaling with the number of confined methanol molecules. As expected, the effect of methane in the non-dipolar MOF is negligible, whereas subtle differences can be observed for the dipolar response of the MOF with rotatable dipolar linker groups. Taking advantage of these anisotropic and guest-molecule-specific confinement effects may open pathways for future sensing applications. Finally, methanol-induced global framework dynamics were observed in both MOFs.<\/jats:p>","DOI":"10.1063\/5.0203820","type":"journal-article","created":{"date-parts":[[2024,5,13]],"date-time":"2024-05-13T09:44:06Z","timestamp":1715593446000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":7,"title":["Dielectric response of metal\u2013organic frameworks as a function of confined guest species investigated by molecular dynamics simulations"],"prefix":"10.1063","volume":"160","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-6149-2146","authenticated-orcid":false,"given":"Babak","family":"Farhadi Jahromi","sequence":"first","affiliation":[{"name":"Computational Materials Chemistry Group, Lehrstuhl f\u00fcr Anorganische Chemie 2, Ruhr-Universit\u00e4t Bochum , Bochum, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1933-3644","authenticated-orcid":false,"given":"Rochus","family":"Schmid","sequence":"additional","affiliation":[{"name":"Computational Materials Chemistry Group, Lehrstuhl f\u00fcr Anorganische Chemie 2, Ruhr-Universit\u00e4t Bochum , Bochum, Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2024,5,13]]},"reference":[{"key":"2024051309425820400_c1","doi-asserted-by":"publisher","first-page":"2334","DOI":"10.1002\/chin.200429230","article-title":"Functional porous coordination polymers","volume":"43","year":"2004","journal-title":"Angew. 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