Carbonato-bridged NiII2LnIII2(LnIII = GdIII, TbIII, DyIII) complexes generated by atmospheric CO2 fixation and their single-molecule-magnet behavior: [(4-CO3)2{NiII(3-MeOsaltn)(MeOH or H2O)LnIII(NO3)}2solvent [3-MeOsaltn = N, N -Bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato]

Atmospheric CO2 fixation of [NiII(3-MeOsaltn)(H2O)2]·2.5H2O [3-MeOsaltn = N,N′-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato], LnIII(NO3)3·6H2O, and triethylamine occurred in methanol/acetone, giving a first series of carbonato-bridged NiII2LnIII2 complexes [(μ4-CO3)2{NiII(3-MeOsaltn)(MeOH)LnIII(NO3)}2] (1Gd, 1Tb, and 1Dy). When the reaction was carried out in acetonitrile/water, it gave a second series of complexes [(μ4-CO3)2{NiII(3-MeOsaltn)(H2O)LnIII(NO3)}2]·2CH3CN·2H2O (2Gd, 2Tb, and 2Dy). For both series, each NiII2LnIII2 structure can be described as two di-μ-phenoxo-bridged NiIILnIII binuclear units bridged by two carbonato CO32– units to form a carbonato-bridged (μ4-CO3)2{NiII2LnIII2} structure. The high-spin NiII ion has octahedral coordination geometry, and the LnIII ion is coordinated by O9 donor atoms from NiII(3-MeOsaltn), bidentate NO3–, and one and two oxygen atoms of two CO32– ions. The NO3– ion for the first series roughly lie on Ln–O(methoxy) bonds and are tilted toward the outsid...