{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T03:27:58Z","timestamp":1760239678861,"version":"build-2065373602"},"reference-count":30,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2020,12,29]],"date-time":"2020-12-29T00:00:00Z","timestamp":1609200000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001711","name":"Schweizerischer Nationalfonds zur F\u00f6rderung der Wissenschaftlichen Forschung","doi-asserted-by":"publisher","award":["200020_182000"],"award-info":[{"award-number":["200020_182000"]}],"id":[{"id":"10.13039\/501100001711","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The preparation, characterization and electrochemical and photophysical properties of a series of desymmetrized heteroleptic [Cu(P^P)(N^N)][PF6] compounds are reported. The complexes incorporate the chelating P^P ligands bis(2-(diphenylphosphanyl)phenyl)ether (POP) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos), and 6-substituted 2,2\u2032-bipyridine (bpy) derivatives with functional groups attached by \u2013(CH2)n\u2013 spacers: 6-(2,2\u2032-bipyridin-6-yl)hexanoic acid (1), 6-(5-phenylpentyl)-2,2\u2032-bipyridine (2) and 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-2,2\u2032-bipyridine (3). [Cu(POP)(1)][PF6], [Cu(xantphos)(1)][PF6], [Cu(POP)(2)][PF6], [Cu(xantphos)(2)][PF6], and [Cu(xantphos)(3)][PF6] have been characterized in solution using multinuclear NMR spectroscopy, and the single crystal structure of [Cu(xantphos)(3)][PF6].0.5Et2O was determined. The conformation of the 6-[2-(4-phenyl-1H-1,2,3,triazol-1-yl)ethyl]-substituent in the [Cu(xantphos)(3)]+ cation is such that the \u03b1- and \u03b2-CH2 units reside in the xanthene \u2018bowl\u2019 of the xantphos ligand. The 6-substituent desymmetrizes the structure of the [Cu(P^P)(N^N)]+ cation and this has consequences for the interpretation of the solution NMR spectra of the five complexes. The NOESY spectra and EXSY cross-peaks provide insight into the dynamic processes operating in the different compounds. For powdered samples, emission maxima are in the range 542\u2013555 nm and photoluminescence quantum yields (PLQYs) lie in the range 13\u201328%, and a comparison of PLQYs and decay lifetimes with those of [Cu(xantphos)(6-Mebpy)][PF6] indicate that the introduction of the 6-substituent is not detrimental in terms of the photophysical properties.<\/jats:p>","DOI":"10.3390\/molecules26010125","type":"journal-article","created":{"date-parts":[[2020,12,29]],"date-time":"2020-12-29T19:55:25Z","timestamp":1609271725000},"page":"125","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Desymmetrizing Heteroleptic [Cu(P^P)(N^N)][PF6] Compounds: Effects on Structural and Photophysical Properties, and Solution Dynamic Behavior"],"prefix":"10.3390","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4862-6371","authenticated-orcid":false,"given":"Marco","family":"Meyer","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7536-2223","authenticated-orcid":false,"given":"Fabian","family":"Brunner","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3631-5210","authenticated-orcid":false,"given":"Alessandro","family":"Prescimone","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4916-4041","authenticated-orcid":false,"given":"Edwin C.","family":"Constable","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8074-0089","authenticated-orcid":false,"given":"Catherine E.","family":"Housecroft","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2020,12,29]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1016\/j.egyr.2019.10.044","article-title":"Luminescent copper(I) complexes as promising materials for the next generation of energy-saving OLED devices","volume":"6","author":"Ravaro","year":"2020","journal-title":"Energy Rep."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Costa, R.D. 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