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Synthesis and X‐Ray Crystallographic Characterisation of Frustum‐Shaped Ligated [Cu 18 H 16 (DPPE) 6 ] 2+ and [Cu 16 H 14 (DPPA) 6 ] 2+ Nanoclusters and Studies on Their H 2 Evolution Reactions
Author(s) -
Li Jiaye,
Ma Howard Z.,
Reid Gavin E.,
Edwards Alison J.,
Hong Yuning,
White Jonathan M.,
Mulder Roger J.,
O'Hair Richard A. J.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705448
Subject(s) - nanoclusters , frustum , dication , crystallography , metal , chemistry , crystal structure , crystal (programming language) , copper , materials science , nanotechnology , geometry , molecule , organic chemistry , mathematics , computer science , programming language
We report new structural motifs for Cu nanoclusters that conceptually represent seed crystals for large face‐centred cubic (FCC) crystal growth. Kinetically controlled syntheses, high resolution mass spectrometry experiments for determination of the dication formulae and crystallographic characterisation were carried out for [Cu 18 H 16 (DPPE) 6 ][BF 4 ][Cl] (DPPE=bis(diphenylphosphino)ethane) and [Cu 16 H 14 (DPPA) 6 ][(BF 4 ) 2 ] (DPPA=bis(diphenylphosphino)amine) polyhydrido nanoclusters, which feature the unprecedented bifrustum and frustum metal‐core architecture in metal nanoclusters. The Cu 18 nanocluster contains two Cu 9 frustum cupolae and the Cu 16 nanocluster has one Cu 9 frustum cupola and a Cu 7 distorted hexagonal‐shape base. Gas‐phase experiments revealed that both Cu 18 H 16 and Cu 16 H 14 cores can spontaneously release H 2 upon removal of one bisphosphine capping ligand.