{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,19]],"date-time":"2025-12-19T09:42:13Z","timestamp":1766137333152,"version":"build-2065373602"},"reference-count":49,"publisher":"Wiley","issue":"15","license":[{"start":{"date-parts":[[2020,2,19]],"date-time":"2020-02-19T00:00:00Z","timestamp":1582070400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100010198","name":"Ministerio de Econom\u00eda, Industria y Competitividad, Gobierno de Espa\u00f1a","doi-asserted-by":"publisher","award":["CTQ2016-76120-P","CTQ2017- 84319-P"],"award-info":[{"award-number":["CTQ2016-76120-P","CTQ2017- 84319-P"]}],"id":[{"id":"10.13039\/501100010198","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003030","name":"Ag\u00e8ncia de Gesti\u00f3 d'Ajuts Universitaris i de Recerca","doi-asserted-by":"publisher","award":["2017 SGR 1123"],"award-info":[{"award-number":["2017 SGR 1123"]}],"id":[{"id":"10.13039\/501100003030","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2020,3,12]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We report the synthesis of an unprecedented mono\u2010gold(I) phosphine complex based on a \u201ctwo\u2010wall\u201d aryl\u2010ethynyl extended calix[4]pyrrole. We describe and compare the binding properties of the parent 10\u03b1,20\u03b1\u2010bis\u2010aryl\u2010ethynyl calix[4]pyrrole ligand and the prepared organometallic compound as receptors for tetraalkylammonium chloride salts in dichloromethane and acetone. We describe the results of <jats:sup>1<\/jats:sup>H\u2005NMR, UV\u2013Vis titrations and isothermal titration calorimetry (ITC) experiments in dichloromethane and acetone, aiming to thermodynamically characterize the formed complexes. The obtained results indicate a noticeable decrease in the binding affinity of the chloride for the mono\u2010gold(I) receptor <jats:bold>1<\/jats:bold> compared to the parent ligand <jats:bold>2<\/jats:bold>. The increase in the negative value of the electrostatic surface potential at the center of the aromatic ring of the gold(I) <jats:italic>meso<\/jats:italic>\u2010aryl\u2010ethynyl substituent serves to explain the observed results and the presence in solution of the chloride complex of <jats:bold>1<\/jats:bold> as a mixture of two conformers.<\/jats:p>","DOI":"10.1002\/chem.201905160","type":"journal-article","created":{"date-parts":[[2020,1,9]],"date-time":"2020-01-09T10:02:15Z","timestamp":1578564135000},"page":"3348-3357","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Influence of the Attachment of a Gold(I) Phosphine Moiety at the Upper Rim of a Calix[4]pyrrole on the Binding of Tetraalkylammonium Chloride Salts"],"prefix":"10.1002","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5088-1243","authenticated-orcid":false,"given":"Qingqing","family":"Sun","sequence":"first","affiliation":[{"name":"Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology (BIST)  Av. Pa\u00efsos Catalans 16 43007 Tarragona Spain"},{"name":"Departament de Qu\u00edmica Anal\u00edtica i Qu\u00edmica Org\u00e1nica Universitat Rovira i Virgili  c\/Marcel l\u00ed Domingo 1 43007 Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2405-0278","authenticated-orcid":false,"given":"Gemma","family":"Aragay","sequence":"additional","affiliation":[{"name":"Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology (BIST)  Av. Pa\u00efsos Catalans 16 43007 Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9491-7140","authenticated-orcid":false,"given":"Andrea","family":"Pinto","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica Inorg\u00e0nica i Org\u00e0nica Secci\u00f3 de Qu\u00edmica Inorg\u00e0nica Universitat de Barcelona  Mart\u00ed i Franqu\u00e8s 1\u201311 08028 Barcelona Spain"},{"name":"Institut de Nanoci\u00e8ncia i Nanotecnologia (IN2UB) Universitat de Barcelona  08028 Barcelona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Elisabet","family":"Aguil\u00f3","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica Inorg\u00e0nica i Org\u00e0nica Secci\u00f3 de Qu\u00edmica Inorg\u00e0nica Universitat de Barcelona  Mart\u00ed i Franqu\u00e8s 1\u201311 08028 Barcelona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1289-1587","authenticated-orcid":false,"given":"Laura","family":"Rodr\u00edguez","sequence":"additional","affiliation":[{"name":"Departament de Qu\u00edmica Inorg\u00e0nica i Org\u00e0nica Secci\u00f3 de Qu\u00edmica Inorg\u00e0nica Universitat de Barcelona  Mart\u00ed i Franqu\u00e8s 1\u201311 08028 Barcelona Spain"},{"name":"Institut de Nanoci\u00e8ncia i Nanotecnologia (IN2UB) Universitat de Barcelona  08028 Barcelona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8377-6610","authenticated-orcid":false,"given":"Pablo","family":"Ballester","sequence":"additional","affiliation":[{"name":"Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology (BIST)  Av. Pa\u00efsos Catalans 16 43007 Tarragona Spain"},{"name":"ICREA  Passeig Llu\u00eds Companys 23 08010 Barcelona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2020,2,19]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja960307r"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/a706280j"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo0016273"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja4021793"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja412098v"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2013.10.036"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1115356108"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2007.07.060"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6SC03554J"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar500157a"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201202777"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200800899"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja064012h"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200462945"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200462945"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2017.08.008"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC10095F"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7DT02732J"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9QO00258H"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/b003536j"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200900422"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cs15123a"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201610762"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201610762"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cc12060c"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201302524"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201302524"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja301900s"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200700112"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6PP00057F"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic300609f"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.8b01993"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2017.08.003"},{"key":"e_1_2_7_31_1","unstructured":"Protonics Softwarehttp:\/\/www.hyperquad.co.uk\/HypSpec.htm."},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01552a016"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.33.8822"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"e_1_2_7_36_1","unstructured":"Gaussian\u200509 Revision\u2005A.02 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery Jr. J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels \u00d6. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT 2009."},{"key":"e_1_2_7_37_1","unstructured":"1H\u2005NMR titrations of model compound6with TBACl and MTOACl in DCM or acetone do not show noticeable changes in the acquired1H\u2005NMR spectra of6before and after the addition of the salts. These findings indicate that Au chloride interactions are not significant."},{"key":"e_1_2_7_38_1","unstructured":"CCDC\u20051965694 and 1965695contain the supplementary crystallographic data for this paper. These data are provided free of charge byThe Cambridge Crystallographic Data Centre."},{"key":"e_1_2_7_39_1","unstructured":"The1H\u2005NMR titrations of the parent ligand2in acetone with the two salts provided identical results (see Supporting Information for details). We concluded that2acts mainly as homotopic receptor for ion-pair binding in acetone and that the stability constant of the anionic chloride complex [Cl\u22822]\u2212is larger than 104\u2009m\u22121."},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201100208"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201100208"},{"key":"e_1_2_7_41_1","first-page":"39","volume-title":"Aromatic Interactions: Frontiers in Knowledge and Application","author":"Frontera A.","year":"2017"},{"key":"e_1_2_7_42_1","unstructured":"1H\u2005NMR titration experiments of1with tetraethylammonium chloride (TEACl) in acetone also supports the presence of two conformers for the chloride complex in solution (see Supporting Information)."},{"key":"e_1_2_7_43_1","unstructured":"The1H\u2005NMR spectrum acquired after the solid\u2013liquid extraction of tetra-methyl ammonium chloride (TMACl) by1dissolved in acetone was similar to the one obtained after the addition of 1\u20132\u2005equivalents of MTOACl to an acetone solution of the same receptor. The1H\u2005NMR spectrum displayed two different sets of proton signals. This observation indicated the presence of the anionic complex in solution as a mixture of two conformers (see Supporting Information)."},{"key":"e_1_2_7_44_1","unstructured":"We also performed ITC experiments of receptors1and2with tetra-ethyl ammonium chloride (TEACl) in acetone. In both cases the binding constant values obtained from the fit of the experimental data to a simple 1:1\u2005binding model are between those determined for MTOACl and TBACl (see Supporting Information)."},{"key":"e_1_2_7_45_1","unstructured":"For some reaction runs the isolation of pure1required multiple precipitations and produced lower yields. This result suggests that the initially isolated pale-yellow solid is a mixture of starting material mono- and bis-gold(I) aryl-ethynyl phosphine complex. An increase in the number of equivalents of AuCl(PTA) (up to 2.3\u2005equiv) allowed the isolation although in low yields (<20\u2009%) of the bis-gold(I) aryl-ethynyl phosphine derivative after multiple precipitations."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201905160","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201905160","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.201905160","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201905160","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T20:21:11Z","timestamp":1760300471000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201905160"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,2,19]]},"references-count":49,"journal-issue":{"issue":"15","published-print":{"date-parts":[[2020,3,12]]}},"alternative-id":["10.1002\/chem.201905160"],"URL":"https:\/\/doi.org\/10.1002\/chem.201905160","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"type":"print","value":"0947-6539"},{"type":"electronic","value":"1521-3765"}],"subject":[],"published":{"date-parts":[[2020,2,19]]},"assertion":[{"value":"2019-11-14","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2020-02-19","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}