Synthesis and characterization of a family of penta- and tetra-manganese(III) complexes derived from an assembly system containing tert-butylphosphonic acid

A family of manganese complexes, Mn 5O 3( t-BuPO 3) 2(MeCOO) 5(H 2O)(phen) 2] ( 1), Mn 5O 3( t-BuPO 3) 2(PhCOO) 5(phen) 2] ( 2), Mn 4O 2( t-BuPO 3) 2(RCOO) 4(bpy) 2] (R = Me, ( 3); R = Ph, ( 4)), NBu (n) 4Mn 4O 2(EtCOO) 3(MeCOO) 4(pic) 2] ( 5), NR' 4Mn 4O 2( i-PrCOO) 7(pic) 2] (R' = Bu (n) , ( 6); R' = Et, ( 7)), were synthesized and characterized. The seven manganese clusters were all prepared from a reaction system containing tert-butylphosphonic acid, Mn(O 2CR) 2 (R = Me, Ph) and NR' 4MnO 4 (R' = Bu (n) , Et) with similar procedures except for using different N-containing ligands (1,10-phenanthroline (phen), 2,2'-bipyridine (bpy) and picolinic acid (picH)) as coligands. The structures of these complexes vary with the N-containing donors. Both the cores of complexes 1 and 2 feature three mu 3-O and two capping t-BuPO 3 (2-) groups bridging five Mn (III) atoms to form a basket-like cage structure. Complexes 3 and 4 both have one Mn 4(mu 3-O) 2] (8+) core with four coplanar Mn (III) atoms disposed in an extended "butterfly-like" arrangement and two capping mu 3- t-BuPO 3 (2-) binding to three manganese centers above and below the Mn 4 plane. Complexes 5, 6, and 7 all possess one Mn 4(mu 3-O) 2] (8+) core just as complexes 3 and 4, but they display a folded "butterfly-like" conformation with the four Mn (III) atoms nonplanar. Thus, the seven compounds are classified into three types, and three representative compounds 1.2H 2O.MeOH.MeCN , 3.6H 2O.2MeCOOH , and 5.0.5H 2O have been characterized by IR spectroscopy, ESI-MS spectroscopy, magnetic measurements and in situ UV-vis-NIR spectroelectrochemical analysis. Magnetic susceptibility measurements reveal the existence of both ferromagnetic and antiferromagnetic interactions between the adjacent Mn (III) ions in compound 1.2H 2O.MeOH.MeCN , and antiferromagnetic interactions in 3.6H 2O.2MeCOOH and 5.0.5H 2O. Fitting the experimental data led to the following parameters: J 1 = -2.18 cm (-1), J 2 = 6.93 cm (-1), J 3 = -13.94 cm (-1), J 4 = -9.62 cm (-1), J 5 = -11.17 cm (-1), g = 2.00 ( 1.2H 2O.MeOH.MeCN ), J 1 = -5.41 cm (-1), J 2 = -35.44 cm (-1), g = 2.13, zJ' = -1.55 cm (-1) ( 3.6H 2O.2MeCOOH ) and J 1 = -2.29 cm (-1), J 2 = -35.21 cm (-1), g = 2.02, zJ' = -0.86 cm (-1) ( 5.0.5H 2O ).