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Surface\u2010protecting ligands play a crucial role in controlling the atomic packing mode of the inner core. The synthesis and total structural determination of the all alkynyl\u2010protected gold nanocluster (NEt<jats:sub>3<\/jats:sub>CH<jats:sub>2<\/jats:sub>Cl)<jats:sub>2<\/jats:sub>[Au<jats:sub>110<\/jats:sub>(C\u2261CC<jats:sub>3<\/jats:sub>H<jats:sub>6<\/jats:sub>Ph)<jats:sub>48<\/jats:sub>] (<jats:bold>Au<jats:sub>110<\/jats:sub>\u20101<\/jats:bold>) are reported. <jats:bold>Au<jats:sub>110<\/jats:sub>\u20101<\/jats:bold> and the previously reported [Au<jats:sub>110<\/jats:sub>(C\u2261CC<jats:sub>6<\/jats:sub>H<jats:sub>4<\/jats:sub>\u20104\u2010CF<jats:sub>3<\/jats:sub>)]<jats:sup>2\u2212<\/jats:sup> (<jats:bold>Au<jats:sub>110<\/jats:sub>\u20102<\/jats:bold>) constitute the largest alkynyl\u2010protected nanocluster quasi\u2010isomers (&gt; 100 metal atoms). Both <jats:bold>Au<jats:sub>110<\/jats:sub><\/jats:bold> consist of an fcc Au<jats:sub>86<\/jats:sub> kernel and a shell of 24 RC\u2261C\u2500Au\u2500C\u2261CR staples, but the specific arrangements are different. The application of the flexible alkynyl ligands creates a significant difference in the face\u2010centered cubic (fcc) kernel structure in <jats:bold>Au<jats:sub>110<\/jats:sub>\u20101<\/jats:bold>, showing a different electronic structure, thermal\u2010 and photo\u2010stability. Transient absorption spectra reveal that <jats:bold>Au<jats:sub>110<\/jats:sub>\u20101<\/jats:bold> still does not show any metallic characteristics, even though it has a smaller energy gap (<jats:italic>E<\/jats:italic>g) than <jats:bold>Au<jats:sub>110<\/jats:sub>\u20102<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/smll.202502106","type":"journal-article","created":{"date-parts":[[2025,4,2]],"date-time":"2025-04-02T08:01:54Z","timestamp":1743580914000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["The Influence of Flexibility of Alkynyl Ligands on the Formation of an Fcc Au<sub>110<\/sub> Nanocluster"],"prefix":"10.1002","volume":"21","author":[{"given":"Feng","family":"Hu","sequence":"first","affiliation":[{"name":"Department of Chemistry Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education) Tsinghua University  Beijing 100084 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gaoyuan","family":"Yang","sequence":"additional","affiliation":[{"name":"Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices Hubei University of Arts and Science  Xiangyang Hubei 441053 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhen\u2010Chao","family":"Long","sequence":"additional","affiliation":[{"name":"Department of Chemistry Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education) Tsinghua University  Beijing 100084 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wan\u2010Qi","family":"Shi","sequence":"additional","affiliation":[{"name":"Department of Chemistry Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education) Tsinghua University  Beijing 100084 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gui\u2010Jie","family":"Liang","sequence":"additional","affiliation":[{"name":"Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices Hubei University of Arts and Science  Xiangyang Hubei 441053 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jia\u2010Qi","family":"Wang","sequence":"additional","affiliation":[{"name":"Fujian Provincial Key Laboratory of Polymer Materials College of Chemistry and Materials Science Fujian Normal University  Fuzhou Fujian 350007 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3764-6409","authenticated-orcid":false,"given":"Quan\u2010Ming","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education) Tsinghua University  Beijing 100084 P. R. 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