Premium
Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball
Author(s) -
Edwards Alison J.,
Dhayal Rajendra S.,
Liao PingKuei,
Liao JianHong,
Chiang MingHsi,
Piltz Ross O.,
Kahlal Samia,
Saillard JeanYves,
Liu C. W.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403324
Subject(s) - copper , hydride , dithiocarbamate , crystallography , octahedron , tetrahedron , molecule , chemistry , atom (system on chip) , ion , crystal structure , metal , organic chemistry , embedded system , computer science
Abstract The syntheses of the first rhombicuboctahedral copper polyhydride complexes [Cu 28 (H) 15 (S 2 CNR) 12 ]PF 6 (NR=N n Pr 2 or aza‐15‐crown‐5) are reported. These complexes were analyzed by single‐crystal X‐ray and one by neutron diffraction. The core of each copper hydride nanoparticle comprises one central interstitial hydride and eight outer‐triangular‐face‐capping hydrides. A further six face‐truncating hydrides form an unprecedented bridge between the inner and outer copper atom arrays. The irregular inner Cu 4 tetrahedron is encapsulated within the Cu 24 rhombicuboctahedral cage, which is further enclosed by an array of twelve dithiocarbamate ligands that subtends the truncated octahedron of 24 sulfur atoms, which is concentric with the Cu 24 rhombicuboctahedron and Cu 4 tetrahedron about the innermost hydride. For these compounds, an intriguing, albeit limited, H 2 evolution was observed at room temperature, which is accompanied by formation of the known ion [Cu 8 (H)(S 2 CNR) 6 ] + upon exposure of solutions to sunlight, under mild thermolytic conditions, and on reaction with weak (or strong) acids.