The first photochromic bimetallic assemblies based on Mn(iii) and Mn(ii) Schiff-base (salpn, dapsc) complexes and pentacyanonitrosylferrate

Abstract

The bimetallic cyano-bridged complexes demonstrating photochromism and magnetism were obtained and studied.

Slow Magnetic Relaxation, Antiferromagnetic Ordering, and Metamagnetism in MnII(H2dapsc)‐FeIII(CN)6Chain Complex with Highly Anisotropic Fe‐CN‐Mn Spin Coupling

“…The Mn II ion has a distorted pentagonal bipyramidal coordination, formed by two oxygen and three nitrogen atoms of the equatorial H 2 dapsc ligand and two axial nitrogen atoms from cyanide bridges. The Mn−O, N bond lengths in the Mn II (H 2 dapsc) moiety (Table S1) are somewhat longer in 1 as compared with relevant bonds in the structures of previously published chain complexes with Mn(H 2 dapsc) . The Mn(H 2 dapsc) fragment is also less flat: the dihedral angle between the two semicarbazone planes defined by atoms O(1), C(1), N(3), N(5), C(4), C(5), N(7) and O(2), C(2), N(4), N(6), C(10), C(9), N(7) is 12.78(9)°.…”

“…However, several important 1D compounds have been synthesized, such as bimetallic chain complexes based on [M(H 2 dapsc)Cl 2 ] 0 (M=Mn II and Fe II ) units in combination with [Fe(CN) 5 NO] 2− , [Mn(CN) 6 ] 3− (M=Mn II ) and [Cr(dapbh)(CN) 2 ] (M=Fe II ). The former compound exhibits photochromism stemming from the nitroprusside anion and the latter are SCMs . The chain complex was also obtained in the reaction between [Fe(H 2 dapbh)Cl 2 ] and [Ni(CN) 4 ] 2− , which showed field‐induced slow magnetic relaxation .…”

Crystal Engineering of Schiff Base Zn(II) and Cd(II) Homo- and Zn(II)M(II) (M = Mn or Cd) Heterometallic Coordination Polymers and Their Ability to Accommodate Solvent Guest Molecules

“…The analysis of the Cambridge Structural Database (CSD, version 2020.2.0) revealed 20 transition metal CPs with this type of ligands [ 13 ]. In most of them, the metal atoms are interconnected by inorganic bridges, such as CN − [ 9 , 12 , 14 ], N 3 − [ 8 ], [Ni(CN) 4 ] 2 − [ 11 , 14 , 15 ], [Fe(CN) 6 ] 3 − [ 16 , 17 , 18 ] and [Mn(CN) 6 ] 3 − [ 19 ], but only in two examples the polymer dimensionality was realized by the ligand terminal arms, isonicotinoylhydrazone [ 10 ] and 2-aminobenzoylhydrazone [ 20 ]. The combination of various 2,6-diacetylpyridine Schiff bases and Zn(II)/Cd(II) metals led to 26 discrete coordination compounds with catalytic [ 21 , 22 ], magnetic [ 23 ], nonlinear optics [ 22 ], photoluminescent [ 24 ] and biological activity [ 25 ].…”

Synthesis, Structure, and Magnetic Properties of 1D {[MnIII(CN)6][MnII(dapsc)]}n Coordination Polymers: Origin of Unconventional Single-Chain Magnet Behavior

“…The pentanuclear [{M­(II)­(L)} 3 {W­(CN) 8 } 2 (H 2 O) 2 ] (M = Ni, Fe, Co; L = dapbh, dapbih, Figure ) and [{Co­(dapbh)} 3 {M­(CN) 6 } 2 (H 2 O) 2 ] (M = Cr, Fe) and trinuclear [{Mn­(dapsc)} 2 {Mo­(CN) 7 }­(H 2 O) 2 ] complexes have been described. ,,, Two of them with [Ni­(dapbh)] 2+ and [Fe­(dapbih)] 2+ are SMMs. , Recently, the first bimetallic chain complexes based on [Mn­(dapsc)] 2+ and [Fe­(dapbh)] 2+ planar units with diamagnetic cyanometallates [Fe­(CN) 5 NO] 2– and [Ni­(CN) 4 ] 2– have been synthesized. The former exhibits photochromism associated with the presence of the nitroprusside anion, and the latter is an SIM and shows slow magnetic relaxation induced by the magnetic field…”