Cyanido-Bridged Fe(III)–Mn(III) Heterobimetallic Materials Built From Mn(III) Schiff Base Complexes and Di- or Tri-Cyanido Fe(III) Precursors

The reaction of [Fe^IIIL­(CN)₃]⁻ (L being bpca = bis­(2-pyridylcarbonyl)­amidate, pcq = 8-(pyridine-2-carboxamido)­quinoline) or [Fe^III(bpb)­(CN)₂]⁻ (bpb = 1,2-bis­(pyridine-2-carboxamido)­benzenate) ferric complexes with Mn^III salen type complexes afforded seven new bimetallic cyanido-bridged Mn­(III)–Fe­(III) systems: [Fe­(pcq)­(CN)₃Mn­(saltmen)­(CH₃OH)]·CH₃OH (<b>1</b>), [Fe­(bpca)­(CN)₃Mn­(3-MeO-salen)­(OH₂)]<b>·</b>CH₃OH<b>·</b>H₂O (<b>2</b>), [Fe­(bpca)­(CN)₃Mn­(salpen)] (<b>3</b>), [Fe­(bpca)­(CN)₃Mn­(saltmen)] (<b>4</b>), [Fe­(bpca)­(CN)₃Mn­(5-Me-saltmen)]·2CHCl₃ (<b>5</b>), [Fe­(pcq)­(CN)₃Mn­(5-Me-saltmen)]·2CH₃OH·0.75H₂O (<b>6</b>), and [Fe­(bpb)­(CN)₂Mn­(saltmen)]·2CH₃OH (<b>7</b>) (with saltmen^2– = <i>N,N</i>′-(1,1,2,2-tetramethylethylene)­bis­(salicylideneiminato) dianion, salpen^2– = <i>N,N</i>′-propylenebis­(salicylideneiminato) dianion, salen^2– = <i>N,N</i>′-ethylenebis­(salicylideneiminato) dianion). Single crystal X-ray diffraction studies were carried out for all these compounds indicating that compounds <b>1</b> and <b>2</b> are discrete dinuclear [Fe­(III)–CN–Mn­(III)] complexes while systems <b>3</b>–<b>7</b> are heterometallic chains with {−NC–Fe­(III)–CN–Mn­(III)} repeating units. These chains are connected through π–π and short contact interactions to form extended supramolecular networks. Investigation of the magnetic properties revealed the occurrence of antiferromagnetic Mn­(III)···Fe­(III) interactions in <b>1</b>–<b>4</b> while ferromagnetic Mn­(III)···Fe­(III) interactions were detected in <b>5</b>–<b>7</b>. The nature of these Mn­(III)···Fe­(III) magnetic interactions mediated by a CN bridge appeared to be dependent on the Schiff base substituent. The packing is also strongly affected by the nature of the substituent and the presence of solvent molecules, resulting in additional antiferromagnetic interdinuclear/interchain interactions. Thus the crystal packing and the supramolecular interactions induce different magnetic properties for these systems. The dinuclear complexes <b>1</b> and <b>2</b>, which possess a paramagnetic <i>S</i>_T = 3/2 ground state, interact antiferromagnetically in their crystal packing. At high temperature, the complexes <b>3</b>–<b>7</b> exhibit a one-dimensional magnetic behavior, but at low temperature their magnetic properties are modulated by the supramolecular arrangement: a three-dimensional antiferromagnetic order with a metamagnetic behavior is observed for <b>3</b>, <b>4</b>, and <b>7</b>, and Single-Chain Magnet properties are detected for <b>5</b> and <b>6