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A relatively unexplored synthetic route in redox-active Mn(II/III) coordination chemistry has been employed toward the preparation of a new mixed-valence Mn II/III 1-D linear chain from the reaction of [Mn III (sacb) 2 ] - precursor with a Mn II source, where sacbH 2 is the Schiff base ligand N -salicylidene-2-amino-5-chlorobenzoic acid. The mononuclear (Pr 2 NH 2 )[Mn III (sacb) 2 ] ( 1 ) compound was obtained in excellent yields (&gt;85%) from the 1:2:3 reaction of Mn(O 2 CMe) 2 ∙4H 2 O, sacbH 2 and Pr 2 NH, respectively. In 1 , the two doubly deprotonated sacb 2- ligands act as O carboxylate ,N imine ,O phenoxide -tridentate chelates, while the second carboxylate O atom of sacb 2- is dangling and H-bonded to the Pr 2 NH 2  + countercation. Complex 1 was subsequently used as a 'ligand' to react stoichiometrically with the 'metal' Mn(NO 3 ) 2 ∙4H 2 O, thus leading to the 1-D coordination polymer {[Mn II Mn III (sacb) 2 (H 2 O) 2 (MeOH) 2 ](NO 3 )} n ( 2 ) in good yields (~50%). The removal of Pr 2 NH 2  + from the vicinity of the [Mn III (sacb) 2 ] - metalloligand has rendered possible (vide infra) the coordination of the second O carboxylate of sacb 2- to neighboring {Mn II (H 2 O) 2 (MeOH) 2 } 2+ units, and consequently the formation of the 1-D polymer 2 . Direct-current (dc) magnetic susceptibility studies revealed the presence of very weak antiferromagnetic exchange interactions between alternating Mn III and Mn II atoms with a coupling constant of J = -0.08 cm -1 for g = 2.00. The combined results demonstrate the potential of the 'metal complexes as ligands' approach to yield new mixed-valence Mn(II/III) coordination polymers with interesting structural motifs and physicochemical properties.

materials

‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain