Syntheses, Crystal Structures, and Magnetic Properties of MnIII(L)phosphinate Complexes (L = meso‐tetraphenylporphyrin or Schiff base). Issue 18 (10th May 2013)

• Record Type: Journal Article
• Authors: Richeter, Sébastien; Larionova, Joulia; Long, Jérôme; van der Lee, Arie; Leclercq, Dominique
• Is Part Of: European journal of inorganic chemistry. Issue 18(2013)
• Page Start: 3206
• Page End: 3216
• Publication Date: 2013-05-10
• Subjects: Manganese -- Magnetic properties -- Porphyrins -- Schiff bases -- Phosphinates; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300246
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The structural organization and magnetic properties of Mn III complexes with meso ‐tetraphenylporphyrin (TPP), bis(3, 5‐di‐ tert ‐butylsalicylidene)ethylenediamine ( t Bu Salen), and bis(salicylidene)ethylenediamine (Salen) capping ligands assembled with phosphinate ligands such as H2 PO2 –, PhHPO2 – and Ph2 PO2 – have been investigated. The structural organization and, thus, the magnetic properties in this series depends on the nature of both the capping and bridging ligands. The hypophosphite ion (H2 PO2 – ) and the diphenylphosphinate ion (Ph2 PO2 – ) act as bridging ligands to form 1D polymeric structures [{Mn(TPP)O2 PH2 }2 · H2 O· EtOH] n and [Mn(Salen)O2 PPh2 ] n, among which only the former presents single chain magnet behaviour; the pronounced nonalignment of the anisotropy axes explains the absence of such behaviour in the latter. The phenylphosphinate ion (PhHPO2 – ) and the diphenylphosphinate ion (Ph2 PO2 – ) act as monodentate ligands in the complexes with t Bu Salen and TPP as capping ligands, respectively. The diphenylphosphinate ion acts as both a bidentate ligand and charge‐compensating anion in [Mn2 ( t Bu Salen)2 (O2 PPh2 )(EtOH)2 + (Ph2 PO2 – )· H2 O]. Abstract : The synthesis of Mn III complexes capped by tetradentate ligands and assembled by phosphinate ligands is reported. The phosphinate coordination mode is influenced by the steric hindrance of both the phosphinate and the tetradentate ligands. Two 1D polymeric structures have been obtained, one of which presents single chain magnet (SCM) behaviour.