Heterometallic complexes combining [MnIII(salpn)]+ and [Fe(CN)6]4− units as the products of reactions between [MnIII(salpn)(H2O)C(CN)3] and [Fe(CN)6]3−/4−Electronic supplementary information (ESI) available: Fig S1-S6. CCDC 986574 (2), 986575 (3) and 986576 (4). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nj00427b

The reaction of [Fe( iii )(CN) 6 ] 3− with neutral [Mn(salpn)(H 2 O)C(CN) 3 ] (salpn: N,N ′-propylenebis(salicylideneiminato)) ( 1 ) produces two new heterometallic complexes [{Mn III (salpn)(H 2 O)} 2 {Mn III (salpn)(H 2 O) 0.7 (CH 3 OH) 0.3 } 2 Fe II (CN) 6 ]· n (H 2 O/CH 3 OH) ( 2 ) and [{Mn III (salpn)} 4 {Mn III (salpn)(H 2 O)} 2 Fe II (CN) 6 ]{C(CN) 3 } 2 ·4H 2 O ( 3 ), which are characterized by single-crystal X-ray diffraction. In this reaction, the [C(CN) 3 ] − ligand reduces Fe( iii ) to Fe( ii ). Complex 3 can be prepared directly using hexacyanoferrate( ii ). One more complex containing the hexacyanoferrate( ii ), [{Mn III (salpn)(CH 3 OH) 0.67 (H 2 O) 0.33 } 6 Fe II (CN) 6 ]{ClO 4 } 2 ·8H 2 O ( 4 ), is obtained in the reaction of [Fe( ii )(CN) 6 ] 4− with the cationic complex [Mn 2 (salpn) 2 (H 2 O) 2 ](ClO 4 ) 2 . The iron( ii ) centers in the complexes 2 and 4 are linked via cyano-bridges with the four and six [Mn III (salpn)] + fragments, respectively. The structure of 3 consists of the cyano-bridged [Mn III 6 Fe II ] repeating units linked by double phenolate bridges into a one-dimensional polymeric chain. The magnetic properties of 3 indicate a ferromagnetic coupling between Mn III centers in the double phenolate-bridged [Mn III (salpn)] 2 dinuclear subunits. Quantum calculations within the Heisenberg-Van Vleck model are performed giving the exchange constant J = 0.64 cm −1 and the zero-field splitting parameter D = −3.5 ± 0.5 cm −1 . The ac-susceptibility obeys the Arrhenius law with the activation energy E a = 11.89 cm −1 . The tricyanomethanide ligand reduces Fe( iii ) to Fe( ii ) yielding the discrete and chain complexes.