There are two main approaches to the synthesis of manganese compounds with phosphonate ligands: by molecular assembly of simple salts and by self-assembly of polynuclear architecture from sustainable building blocks. In this work we investigated the possibility of the formation of homo- and heterovalent manganese pivalate-phosphonate complexes by self-assembly from a mixture of simple available reagents. Interaction of MnCl2·4H2O, NaPiv with H2PO3But leads to the formation of manganese(II) complexes: [(HPiv)12MnII 4(O3PBut )4] (1), [(HPiv)8MnII 10(Cl)4(O3PBut )4(Piv)8] (2) and [(HPiv)8(H2O)8MnII 20(OH)2(Cl)2(O3PBut )12(Piv)12] (3). Metal core of tetranuclear complex 1 can be described as a heterocubane (Mn…Mn 4.799(2)- 4.844(2) Å, P…P 4.685(4)-4.732(4) Å). Mixed-valent complexes: [(MeOH)2MnII 5MnIII 11 (O)8(OMe)5(O3PBut )7(Piv)8] (4) and [(HPiv)2(MeOH)2 (H2O)2Na4(Piv)2][(MeOH)2MnII 3MnIII 12(O)8(Cl)2(OMe)4 (O3PBut )10(Piv)2] (5) are formed on oxidation of the starting reaction mixture. Additional oxidation of compound 4 by KMnO4 leads to the formation of K·[MnIII 12(O)7(CH3O)4 (ButPO3)3(Piv)13] (6), which "encapsulates" potassium cation like cryptands (Fig. 1). In molecules 4-6 MnIII centers show the typical Jahn-Teller distortion of the octahedral coordination environment: Mnaxis-O 2.151(4)- 2.354(4), Mn-O 1.838(4)-1.999(4) Å (for 4); Mnaxis-O 2.171(4)-2.677(2), Mn-O 1.869(5)-1.962(4) Å and MnaxisO 1.902(5)-1.958(4), Mn-O 2.016(5)-2.068(6) Å (for 5); (Mnaxis-O 2.023(8)-2.427(8) and 1.854(6)-2.022(6) Å) and (Mnaxis-O 1.824(7)-1.997(1) and 2.078(5)-2.270(1) Å) (for 6). According to susceptibility data for 1–3, antiferromagnetic exchange interactions predominate in these compounds, which leads to a monotonic decrease of μeff value 11.76- 7.40 μB (for 1), 17.26-4.25 μB (for 2), 25.11-7.77 μB (for 3) with decreasing temperature in temperature range 300-2 K. It was found that exchange spin-spin antiferromagnetic interactions between Mn(II) ions are equivalent in complex 1 (JMn–Mn = –0.097(1) см-1 , gMn = 1.993(1)). The character of µeff(T) dependency for complex 4 and positive θ value (3.80.3 K) indicates on ferromagnetic exchange interactions between the paramagnetic centers.figureFig. 1. Molecule of complex 6 (But -substituents of pivalates and hydrogen atoms are not shown).