Synthesis and X-Ray Crystallographic Characterisation of Frustum-Shaped Ligated [Cu18H16(DPPE)6]2+and [Cu16H14(DPPA)6]2+Nanoclusters and Studies on Their H2Evolution Reactions Academic Article uri icon

abstract

  • 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 [Cu18 H16 (DPPE)6 ][BF4 ][Cl] (DPPE=bis(diphenylphosphino)ethane) and [Cu16 H14 (DPPA)6 ][(BF4 )2 ] (DPPA=bis(diphenylphosphino)amine) polyhydrido nanoclusters, which feature the unprecedented bifrustum and frustum metal-core architecture in metal nanoclusters. The Cu18 nanocluster contains two Cu9 frustum cupolae and the Cu16 nanocluster has one Cu9 frustum cupola and a Cu7 distorted hexagonal-shape base. Gas-phase experiments revealed that both Cu18 H16 and Cu16 H14 cores can spontaneously release H2 upon removal of one bisphosphine capping ligand.

authors

  • Li, J
  • Ma, HZ
  • Reid, GE
  • Edwards, AJ
  • Hong, Yuning
  • White, JM
  • Mulder, RJ
  • O'Hair, RAJ

publication date

  • 2018