Unusual core engineering on a copper hydride nanoball. Issue 7 (25th January 2023)

• Record Type: Journal Article
• Authors: Silalahi, Rhone P. Brocha; Liao, Jian-Hong; Tseng, Yu-Fang; Chiu, Tzu-Hao; Kahlal, Samia; Saillard, Jean-Yves; Liu, C. W.
• Is Part Of: Dalton transactions. Volume 52:Issue 7(2023)
• Page Start: 2106
• Page End: 2114
• Publication Date: 2023-01-25
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt03449b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Through unexpected core engineering, modification of the inner Cu4 tetrahedron in [Cu28 H15 ] + into a Cu3 triangle in [Cu27 H15 ] can be achieved keeping the shell of the Cu24 rhombicuboctahedron intact. Abstract : A neutral polyhydrido copper cluster, [Cu27 H15 {S2 CN n Bu2 }12 ] (abbreviated as [Cu27 H15 ]), was prepared by the reaction of dithiocarbamates (dtc), Cu(i ) salts and NaBH4 . The isolated cluster provides insights into core engineering, demonstrating its novel ability to reversibly add or remove one copper atom from the cluster core. Single-crystal X-ray analysis reveals that the new core–shell structure exhibits a Cu24 rhombicuboctahedral outer cage and an inner Cu3 triangular kernel. The two core–shell clusters, [Cu27 H15 {S2 CN n Bu2 }12 ] and previously published [Cu28 H15 (S2 CN n Bu2 )12 ] + (abbreviated as [Cu28 H15 ] + ), are only differentiated by one copper atom in their inner core. Importantly, we demonstrate core engineering with the controllable reversible transition between an irregular Cu4 tetrahedron and a Cu3 triangle, whilst maintaining their outer Cu24 shell intact. The 15 hydride atoms in [Cu27 H15 ], coordinated in three different modes, are co-incident with the hydride positions in [Cu28 H15 ] + . The degradation of [Cu27 H15 ] in solution or the addition of one eq. of Cu(i ) ions leads to the conversion of [Cu27 H15 ] into [Cu28 H15 ] +, while the reverse transformation can be achieved by the addition of either formic acid or a reducing agent to [Cu28 H15 ] + . A dicationic species was observed in the ESI mass spectrum, and the composition is formulated as [Cu56 H30 (S2 CN n Bu2 )24 ] 2+, a dimer of [Cu27 H15 (S2 CN n Bu2 )12 + Cu + ]2 2+ . The dimeric species was further explored by DFT calculations, suggesting that the lowest energy structure consists of a [Cu28 H15 ] + and a [Cu27 H15 ] cluster connected through one Cu + atom bridge. As a result, [Cu27 H15 ] is considered an intermediate species in the formation of the more stable [Cu28 H15 ] + nanoball.