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The electronic properties were investigated with electrochemical and photophysical techniques, in parallel with three reference compounds, namely, the DCNQ derivative alone, the DCNQ\u2010based phenanthroline ligand, and an analogue Cu<jats:sup>I<\/jats:sup> complex lacking the DCNQ moiety. In all the systems containing the DCNQ unit, the lowest electronic excited states are centered thereon, with the singlet level (S<jats:sub>1<\/jats:sub>) located at about 1.0\u2005eV, as suggested by TDDFT calculations. Accordingly, in the DCNQ\u2010equipped rotaxane, the typical metal\u2010to\u2010ligand charge\u2010transfer luminescence of the Cu<jats:sup>I<\/jats:sup> center is totally quenched. Ultrafast transient absorption and emission studies show that, in the rotaxane, the final sink of photoinduced processes is the lowest singlet state of the DCNQ moiety (S<jats:sub>1<\/jats:sub>), which exhibits strong charge\u2010transfer character and a lifetime of 0.4\u2005ps. Its deactivation leads to population of another excited state with a lifetime of 1.3\u2005ps, which can be the related triplet state (T<jats:sub>1<\/jats:sub>) or a vibrationally hot level (hot\u2010S<jats:sub>0<\/jats:sub>). Notably, S<jats:sub>1<\/jats:sub> also shows stimulated fluorescence in the near\u2010infrared (NIR) region between 1100 and 1500\u2005nm, corroborating the TDDFT prediction. This unusual finding opens up the study of ultrashort\u2010lived NIR luminescence in organic donor\u2013acceptor systems.<\/jats:p>","DOI":"10.1002\/chem.201801161","type":"journal-article","created":{"date-parts":[[2018,5,4]],"date-time":"2018-05-04T08:33:36Z","timestamp":1525422816000},"page":"10422-10433","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Unconventional Synthesis of a Cu<sup>I<\/sup> Rotaxane with a Superacceptor Stopper: Ultrafast Excited\u2010State Dynamics and Near\u2010Infrared Luminescence"],"prefix":"10.1002","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5421-9556","authenticated-orcid":false,"given":"Yann","family":"Trolez","sequence":"first","affiliation":[{"name":"Laboratory of Organic Chemistry ETH Zurich, H\u00f6nggerberg, HCI  8093 Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aaron D.","family":"Finke","sequence":"additional","affiliation":[{"name":"Laboratory of Organic Chemistry ETH Zurich, H\u00f6nggerberg, HCI  8093 Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fabio","family":"Silvestri","sequence":"additional","affiliation":[{"name":"Laboratory of Organic Chemistry ETH Zurich, H\u00f6nggerberg, HCI  8093 Zurich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9806-1957","authenticated-orcid":false,"given":"Filippo","family":"Monti","sequence":"additional","affiliation":[{"name":"Istituto per la Sintesi Organica e la Fotoreattivit\u00e1 Consiglio Nazionale delle Ricerche  Via P. 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