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The assembly process involves in situ comproportionation reaction between Cu<jats:sup>2+<\/jats:sup> and Cu<jats:sup>0<\/jats:sup> and the formation of two different clusters is controlled by reactants concentration. The clusters consist of Cu<jats:sub>15<\/jats:sub> and Cu<jats:sub>16<\/jats:sub> cores co\u2010stabilized by strong by \u03c3\u2010 and \u03c0\u2010bonded <jats:italic>tert<\/jats:italic>\u2010butylethynide and CF<jats:sub>3<\/jats:sub>COO<jats:sup>\u2212<\/jats:sup> (together with methanol molecule in <jats:bold>2<\/jats:bold>). Their stabilities in solution were confirmed using electrospray ionization mass spectrometry in which the cluster core remains intact for <jats:bold>1<\/jats:bold> in chloroform and acetone, and for <jats:bold>2<\/jats:bold> in acetonitrile. Strong thermochromic luminescence in the near infrared (NIR) region was observed in the solid\u2010state. Of particular interest, the emission maximum of <jats:bold>1<\/jats:bold> is red\u2010shifted from 710\u2005nm at 298\u2005K to 793\u2005nm at 93\u2005K, along with a 17\u2010fold fluorescence enhancement. In contrast, <jats:bold>2<\/jats:bold> exhibits red shift from 298 to 123\u2005K followed by blue shift from 123 to 93\u2005K. The emission wavelength was correlated with the structural parameters using variable\u2010temperature X\u2010ray single\u2010crystal analyses. The rich cuprophilic interaction plays a significant role in the formation of <jats:sup>3<\/jats:sup>LMCT (<jats:italic>t<\/jats:italic>BuC\u2261C\u2192Cu<jats:sub>x<\/jats:sub>) excited state mixed with cluster\u2010centered (<jats:sup>3<\/jats:sup>CC) characters, which can be considerably influenced by temperature, leading to thermochromic luminescence. The present work provides 1)\u2005a new synthetic protocol for the high\u2010nuclear Cu<jats:sup>I<\/jats:sup>\u2013alkynyl clusters; 2)\u2005a comprehensive insight into the mechanism of thermochromic luminescence; 3)\u2005unusual emissive materials with the characters of NIR and thermochromic luminescence simultaneously.<\/jats:p>","DOI":"10.1002\/chem.201603797","type":"journal-article","created":{"date-parts":[[2016,10,13]],"date-time":"2016-10-13T14:26:56Z","timestamp":1476368816000},"page":"17619-17626","source":"Crossref","is-referenced-by-count":89,"title":["High\u2010Nuclear Organometallic Copper(I)\u2013Alkynide Clusters: Thermochromic Near\u2010Infrared Luminescence and Solution Stability"],"prefix":"10.1002","volume":"22","author":[{"given":"Hong\u2010Yan","family":"Zhuo","sequence":"first","affiliation":[{"name":"Key Lab for Colloid and Interface Chemistry of Education Ministry School of Chemistry and Chemical Engineering Shandong University  Jinan 250100 P. R. 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