A MnII4 cubane and a novel MnII 10MnIII4 cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry

Constantinos C. Stoumpos, Ian A. Gass, Constantinos J. Milios, Nikolia Lalioti, Aris Terzis, Guillem Aromí, Simon J. Teat, Euan K. Brechin, Spyros P. Perlepes

Research output: Contribution to journalArticlepeer-review

43 Scopus citations


The employment of di-2-pyridyl ketone, (py)2CO, in manganese(ii) acetate chemistry is reported. The syntheses, crystal structures and magnetochemical characterisation are described for [MnII 4(O2CMe)4{(py)2C(OH)O}4] (1) and [MnII10MnIII4O 4(O2CMe)20{(py)2C(OH)O} 4] (2), where (py)2C(OH)O- is the monoanion of the gem-diol form of the ligand. The reaction of Mn(O2CMe) 2·4H2O with one equivalent of (py)2CO in Me2CO gives 1. Complex 2 was obtained from the 1: 1 reaction, in EtOH, between Mn(O2CMe)2·4H2O and (py)2CO in the presence of NEt3. The tetranuclear molecule 1 has a cubane topology with the MnII and the deprotonated oxygen atoms from the η131: μ3 ligands occupying alternate vertices of the cube. The core of 2 consists of two mixed valence cubane {MnII2Mn III23-O)23- OR″)2}4+ subunits that are linked through an unusual {MnII612:μ-O 2CMe)622: μ3-O2CMe)2}4+ moiety via twelve η11:μ MeCO2- groups. Some suggestions have been made concerning the possible assembly of 2 from 1. The magnetic properties of 1 in the 300-5 K range have been modelled with two J values, which reveal weak antiferromagnetic interactions within the molecule. Complex 2 has a low spin ground state. This work demonstrates the flexibility, versatility and synthetic potential of combining (py)2CO with carboxylate ligands.

Original languageEnglish (US)
Pages (from-to)307-317
Number of pages11
JournalDalton Transactions
Issue number2
StatePublished - 2009

ASJC Scopus subject areas

  • Inorganic Chemistry


Dive into the research topics of 'A Mn<sup>II</sup><sub>4</sub> cubane and a novel Mn<sup>II</sup> <sub>10</sub>Mn<sup>III</sup><sub>4</sub> cluster from the use of di-2-pyridyl ketone in manganese acetate chemistry'. Together they form a unique fingerprint.

Cite this