Syntheses, Crystal Structures, and Magnetic Properties of MnIII(L)phosphinate Complexes (L = meso-tetraphenylporphyrin or Schiff base)

• Published in: European journal of inorganic chemistry Vol. 2013; no. 18; pp. 3206 - 3216
• Main Authors: Richeter, Sébastien, Larionova, Joulia, Long, Jérôme, van der Lee, Arie, Leclercq, Dominique
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.06.2013; WILEY‐VCH Verlag; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Subjects: Chemical Sciences; Coordination chemistry; Magnetic properties; Manganese; Phosphinates; Porphyrins; Schiff bases
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201300246

The structural organization and magnetic properties of MnIII complexes with meso‐tetraphenylporphyrin (TPP), bis(3,5‐di‐tert‐butylsalicylidene)ethylenediamine (tBuSalen), and bis(salicylidene)ethylenediamine (Salen) capping ligands assembled with phosphinate ligands such as H2PO2–, PhHPO2– and Ph2PO2– 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 (H2PO2–) and the diphenylphosphinate ion (Ph2PO2–) act as bridging ligands to form 1D polymeric structures [{Mn(TPP)O2PH2}2·H2O·EtOH]n and [Mn(Salen)O2PPh2]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 (Ph2PO2–) act as monodentate ligands in the complexes with tBuSalen and TPP as capping ligands, respectively. The diphenylphosphinate ion acts as both a bidentate ligand and charge‐compensating anion in [Mn2(tBuSalen)2(O2PPh2)(EtOH)2+(Ph2PO2–)·H2O]. The synthesis of MnIII 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.