Control of clustering behavior in anionic cerium(iii) corrole complexes: from oligomers to monomers

Abstract

The first synthesis of anion capped cerium corrole complexes is reported. Unusual clustering of the lanthanide corrole units has been found and the degree of aggregation can be controlled by the choice of the capping ligand. A polymeric structure 1a, with the general formula [Cor–Ce(THF)–Cp–Na]_n (Cor = 5,15-bis(2,4,6-trimethylphenyl)-10-(4 methoxyphenyl)-corrole, THF = tetrahydrofuran), is formed using sodium cyclopentadienide (NaCp) and a dimeric structure 2a, with the general formula [Cor–Ce–Tp]₂, is formed when potassium tris(pyrazolyl)borate (KTp) is used. Encapsulation of the counter-cation leads to the isolation of the monomeric structures 1b and 2b, with the general formulas [AM(2.2.2-cryptand)][Cor–Cp–X] (AM = Na or K, X = Cp or Tp). The structural and spectroscopic properties of the complexes have been investigated.