Hierarchical assembly of discrete copper(II) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

Jack K. Clegg, Feng Li, Katrina A. Jolliffe, Leonard F. Lindoy*, George V. Meehan, Simon Parsons, Peter A. Tasker, Fraser J. White

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The sequential interaction of preformed [Cu2(L111)2(THF)2] (where H2L111 is 1,1-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione incorporating a 1,3-phenylene linker between its two β-diketone domains) and [Cu2(L444)2] · 2H2O (where H2L444 is 1,1-(4,4'-oxybiphenylene)-bis(4,4-dimethylpentane-1,3-dione) incorporating a flexible oxybiphenylene linkage between the two β-diketone groups) with the potentially difunctional aliphatic non-planar co-ligands, N-methylpiperazine (mpip), N,N'-dimethylpiperazine (dmpip) and 1,4-thiomorpholine (thiomorph) is reported. A series of extended molecular assemblies exhibiting a range of di- and tetranuclear assemblies were obtained and their X-ray structures determined. Dinuclear [Cu2(L111)2(mpip)2] · 2mpip incorporates two 5-coordinate, square pyramidal metal centres as does tetranuclear [{Cu2(L111)2}2(dmpip)2] · 2dmpip. In contrast, dinuclear [Cu2(L111)2(dmpip)4] · dmpip and [{Cu2(L111)2}2(thiomorph)4] · 3thiomorph each contain two 5-coordinate and two 6-coordinate centres. Each of [Cu2(L444)2(THF)2] · 2THF and Cu2(L444)2(mpip)2] · H2O incorporate only 5-coordinate metal centres, with the latter complex forming a one-dimensional hydrogen bonded ribbon-like structure directed along the crystallographic a-axis. In keeping with the documented tendency for the smallest, least strained assembly to form in supramolecular self-assembly processes, the incorporation of the flexible "oxy" linkage between the 4,4'-linked phenylene rings of H2L333 results in generation of a dinuclear [Cu2L22] species rather than a trinuclear (triangular) [Cu3L333] species of the type formed by the more rigid bis-beta-diketonato ligand analogue in which the biphenylene rings separating the β-diketone domains are directly coupled in their 4,4' positions.

Original languageEnglish
Pages (from-to)14315-14323
Number of pages9
JournalDalton Transactions
Volume42
Issue number39
DOIs
Publication statusPublished - 21 Oct 2013

Keywords

  • SUPRAMOLECULAR CHEMISTRY
  • BIS(BETA-DIKETONATE) LIGANDS
  • MACROCYCLIC COMPLEXES
  • H-1-NMR SPECTROSCOPY
  • DIKETONATO LIGANDS
  • SOLVENT-EXTRACTION
  • CRYSTAL-STRUCTURES
  • BUILDING-BLOCKS
  • BETA-DIKETONES
  • ION CHEMISTRY

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