{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,15]],"date-time":"2026-05-15T13:15:52Z","timestamp":1778850952068,"version":"3.51.4"},"reference-count":132,"publisher":"Wiley","issue":"66","license":[{"start":{"date-parts":[[2017,9,21]],"date-time":"2017-09-21T00:00:00Z","timestamp":1505952000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001711","name":"Schweizerischer Nationalfonds zur F\u00f6rderung der Wissenschaftlichen Forschung","doi-asserted-by":"publisher","award":["200020_159881\/1"],"award-info":[{"award-number":["200020_159881\/1"]}],"id":[{"id":"10.13039\/501100001711","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,11,27]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Access to reliable values of the thermodynamic constants <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201703184-math-0001.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201703184:chem201703184-math-0001\"\/>\n, which control simple host\u2013guest ([HG]) association, is crucial in medicine, biology, pharmacy, and chemistry, since the optimum concentration of an effector (i.e., a drug) acting on a receptor is set to <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201703184-math-0002.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201703184:chem201703184-math-0002\"\/>\n. Intermolecular association between charged species in polar solvents, for which water is the archetype, largely obeys this principle. Any deviation from ideality, which alters the speciation in solution, is mastered by the Debye\u2013H\u00fcckel theory of ionic atmosphere. Much less is known for related association reactions involving neutral species in non\u2010polar (lipophilic) media such as membranes, bilayers, or organic polymers. Taking the intermolecular association between [La(hfa)<jats:sub>3<\/jats:sub>dig] guest (hfa=hexafluoroacetylacetonate, dig=2\u2010{2\u2010methoxyethoxy}ethane) and tridentate polyaromatic host receptors <jats:bold>L1<\/jats:bold>\u2013<jats:bold>L3<\/jats:bold> in dichloromethane as a proof\u2010of\u2010concept, we show that the progress of the association reactions, as measured by the increase in the mole fraction of occupied sites of the receptors, disrupt the chemical potential of the solvent to such an extent that <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem201703184-math-0003.png\" xlink:title=\"urn:x-wiley:09476539:media:chem201703184:chem201703184-math-0003\"\/>\n may seemingly be shifted by two orders of magnitude, thus leading to erroneous dose\u2010response prescriptions. A simple chemical model, which considers a subset of solvent molecules in surface contact with the partners of the association reaction, restores reliable access to true and interpretable thermodynamic constants. The concomitant emergence of a concentration\u2010dependent corrective parameter reestablishes satisfying dose\u2010dependent response under real conditions. This \u201ccomplement\u201d to the law of mass action offers a simple method for safely taking care of the non\u2010predictable variations of the activity coefficients of the various partners when host\u2013guest reactions are conducted in non\u2010polar media.<\/jats:p>","DOI":"10.1002\/chem.201703184","type":"journal-article","created":{"date-parts":[[2017,8,8]],"date-time":"2017-08-08T07:22:39Z","timestamp":1502176959000},"page":"16787-16798","source":"Crossref","is-referenced-by-count":21,"title":["Chemical Potential of the Solvent: A Crucial Player for Rationalizing Host\u2013Guest Affinities"],"prefix":"10.1002","volume":"23","author":[{"given":"Karine","family":"Baudet","sequence":"first","affiliation":[{"name":"Department of Inorganic, Analytical and Applied Chemistry University of Geneva  30 quai E. Ansermet 1211 Geneva 4 Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sebastiano","family":"Guerra","sequence":"additional","affiliation":[{"name":"Department of Inorganic, Analytical and Applied Chemistry University of Geneva  30 quai E. Ansermet 1211 Geneva 4 Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7064-8548","authenticated-orcid":false,"given":"Claude","family":"Piguet","sequence":"additional","affiliation":[{"name":"Department of Inorganic, Analytical and Applied Chemistry University of Geneva  30 quai E. Ansermet 1211 Geneva 4 Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2017,9,21]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19981102)37:20<2754::AID-ANIE2754>3.0.CO;2-3"},{"key":"e_1_2_7_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19981016)110:20<2908::AID-ANGE2908>3.0.CO;2-2"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja038223n"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300644"},{"key":"e_1_2_7_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200300644"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/b412510j"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr500344e"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.6b00276"},{"key":"e_1_2_7_8_1","unstructured":"\u00a0"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/B612543N"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/B710951M"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200800583"},{"key":"e_1_2_7_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200800583"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp806859w"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200802947"},{"key":"e_1_2_7_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200802947"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00111"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00583"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6OB01303A"},{"key":"e_1_2_7_17_1","unstructured":"\u00a0"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja038396c"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp027833r"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200500290"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200500289"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/b613758j"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/b518461d"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cc00811g"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CP00584A"},{"key":"e_1_2_7_26_1","unstructured":"\u00a0"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01552a035"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/ed055p489"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp0740705"},{"key":"e_1_2_7_30_1","unstructured":"\u00a0"},{"key":"e_1_2_7_31_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0CS00062K"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CC03888C"},{"key":"e_1_2_7_33_1","unstructured":"\u00a0"},{"key":"e_1_2_7_34_2","doi-asserted-by":"publisher","DOI":"10.1002\/poc.610050815"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39920000838"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1039\/b413971b"},{"key":"e_1_2_7_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar040223k"},{"key":"e_1_2_7_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200902490"},{"key":"e_1_2_7_38_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200902490"},{"key":"e_1_2_7_39_1","unstructured":"\u00a0"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201004201"},{"key":"e_1_2_7_40_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201004201"},{"key":"e_1_2_7_41_2","first-page":"1","volume":"50","author":"di Stefano S.","year":"2016","journal-title":"Adv. Phys. Org. Chem."},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00063D"},{"key":"e_1_2_7_43_1","unstructured":"\u00a0"},{"key":"e_1_2_7_44_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.21.4.186"},{"key":"e_1_2_7_45_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-2836(63)80091-1"},{"key":"e_1_2_7_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/bi049393v"},{"key":"e_1_2_7_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr500495x"},{"key":"e_1_2_7_48_1","unstructured":"\u00a0"},{"key":"e_1_2_7_49_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200702075"},{"key":"e_1_2_7_49_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200702075"},{"key":"e_1_2_7_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar900077c"},{"key":"e_1_2_7_51_2","doi-asserted-by":"publisher","DOI":"10.1039\/b819333a"},{"key":"e_1_2_7_52_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs15302e"},{"key":"e_1_2_7_53_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35254K"},{"key":"e_1_2_7_54_1","unstructured":"\u00a0"},{"key":"e_1_2_7_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201208397"},{"key":"e_1_2_7_55_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201208397"},{"key":"e_1_2_7_56_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201409399"},{"key":"e_1_2_7_56_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201409399"},{"key":"e_1_2_7_57_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00163K"},{"key":"e_1_2_7_58_1","unstructured":"\u00a0"},{"key":"e_1_2_7_59_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4615-1223-3_2"},{"key":"e_1_2_7_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp010320k"},{"key":"e_1_2_7_61_2","doi-asserted-by":"publisher","DOI":"10.1039\/B413603A"},{"key":"e_1_2_7_62_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cocis.2006.08.004"},{"key":"e_1_2_7_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp301164f"},{"key":"e_1_2_7_64_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp311812a"},{"key":"e_1_2_7_65_1","unstructured":"\u00a0"},{"key":"e_1_2_7_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja982909b"},{"key":"e_1_2_7_67_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT03419E"},{"key":"e_1_2_7_68_1","unstructured":"\u00a0"},{"key":"e_1_2_7_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9006113"},{"key":"e_1_2_7_70_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6DT04515D"},{"key":"e_1_2_7_71_1","unstructured":"\u00a0"},{"key":"e_1_2_7_72_2","doi-asserted-by":"publisher","DOI":"10.1039\/a827447z"},{"key":"e_1_2_7_73_2","doi-asserted-by":"publisher","DOI":"10.1039\/b107118c"},{"key":"e_1_2_7_74_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200351634"},{"key":"e_1_2_7_74_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200351634"},{"key":"e_1_2_7_75_1","unstructured":"\u00a0"},{"key":"e_1_2_7_76_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2009.12.001"},{"key":"e_1_2_7_77_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00188E"},{"key":"e_1_2_7_77_3","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00067J"},{"key":"e_1_2_7_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b00700"},{"key":"e_1_2_7_79_2","doi-asserted-by":"publisher","DOI":"10.1039\/C7SC00739F"},{"key":"e_1_2_7_80_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp402632a"},{"key":"e_1_2_7_81_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF02648369"},{"key":"e_1_2_7_82_1","first-page":"9","volume-title":"Phys. Chem.","author":"Atkins P.","year":"2010"},{"key":"e_1_2_7_83_1","unstructured":"\u00a0"},{"key":"e_1_2_7_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic4030525"},{"key":"e_1_2_7_85_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5DT01842K"},{"key":"e_1_2_7_86_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201600857"},{"key":"e_1_2_7_87_1","unstructured":"\u00a0"},{"key":"e_1_2_7_88_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200602227"},{"key":"e_1_2_7_88_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200602227"},{"key":"e_1_2_7_89_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200900904"},{"key":"e_1_2_7_90_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201604075"},{"key":"e_1_2_7_91_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102827"},{"key":"e_1_2_7_92_1","first-page":"75","volume":"18","author":"Kang S.-J.","year":"1997","journal-title":"Bull. Korean Chem. Soc."},{"key":"e_1_2_7_93_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200300354"},{"key":"e_1_2_7_94_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja206806t"},{"key":"e_1_2_7_95_1","unstructured":"\u00a0"},{"key":"e_1_2_7_96_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201200516"},{"key":"e_1_2_7_96_3","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201300177"},{"key":"e_1_2_7_97_1","unstructured":"\u00a0"},{"key":"e_1_2_7_98_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600251"},{"key":"e_1_2_7_99_2","doi-asserted-by":"publisher","DOI":"10.1021\/om1000327"},{"key":"e_1_2_7_100_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0dt00278j"},{"key":"e_1_2_7_101_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol3019665"},{"key":"e_1_2_7_102_1","unstructured":"\u00a0"},{"key":"e_1_2_7_103_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cp40083a"},{"key":"e_1_2_7_104_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4DT02657H"},{"key":"e_1_2_7_105_1","unstructured":"\u00a0"},{"key":"e_1_2_7_106_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1750930"},{"key":"e_1_2_7_107_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1750971"},{"key":"e_1_2_7_108_2","first-page":"2","volume-title":"Polymer Blends","year":"1978"},{"key":"e_1_2_7_109_1","unstructured":"\u00a0"},{"key":"e_1_2_7_110_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19990503)5:5<1643::AID-CHEM1643>3.0.CO;2-T"},{"key":"e_1_2_7_111_2","doi-asserted-by":"publisher","DOI":"10.1039\/b102914m"},{"key":"e_1_2_7_112_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201503420"},{"key":"e_1_2_7_113_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2016.11.013"},{"key":"e_1_2_7_114_1","unstructured":"\u00a0"},{"key":"e_1_2_7_115_2","first-page":"1","volume-title":"Lanthanide Probes in Life, Chemical and Earth Science","author":"Choppin G. R.","year":"1989"},{"key":"e_1_2_7_116_2","first-page":"18","volume-title":"Handbook on the Physics and Chemistry of Rare Earths","author":"Choppin G. R.","year":"1994"},{"key":"e_1_2_7_117_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic701337u"},{"key":"e_1_2_7_118_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2011.07.010"},{"key":"e_1_2_7_119_2","first-page":"47","volume-title":"Handbook on the Physics and Chemistry of Rare Earths","author":"Piguet C.","year":"2015"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201703184","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201703184","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:37:23Z","timestamp":1760269043000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201703184"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,9,21]]},"references-count":132,"journal-issue":{"issue":"66","published-print":{"date-parts":[[2017,11,27]]}},"alternative-id":["10.1002\/chem.201703184"],"URL":"https:\/\/doi.org\/10.1002\/chem.201703184","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,9,21]]}}}