Network-Selectivity, Magnetism, and Proton Conduction of 2-D and 3-D Metal-Organic Frameworks of the Constituents {P(CH2OH)4}+/MII (MnII, FeII, or CoII)/[CrIII(ox)3]3-

Two types of metal-organic frameworks (MOFs), including {P(CH2OH)(4)}(6)[MnII3{CrIII(ox)(3)}(4)]center dot 10H(2)O center dot 2EtOH (1) and {P(CH2OH)(4)}[MIICrIII(ox)(3)]center dot H2O (M = Fe (2), and Co (3)), are selectively formed by a reaction of {P(CH2OH)(4)}Br, MCl2, and (NH4)(3)[Cr(ox)(3)]. 1 has the 3-D anionic framework, [Mn-3{Cr(ox)(3)}(4)](n)(6n-), consisting of the Mn4Cr4 octagonal and Mn6Cr6 dodecagonal channels, in which {P(CH2OH)(4)}+ ions and the solvation molecules (H2O and EtOH) are accommodated. 2 and 3 have a 2-D network of oxalate-bridged bimetallic sheets with an intercalation of {P(CH2OH)(4)}(+) ions. Magnetic studies revealed ferromagnetic ordering in all the MOFs, with T-C = 5.6 K for 1, 10.6 K for 2, and 12.2 K for 3. The {P(CH2OH)(4)}(+) ions in the MOFs promote proton transfer via the vehicle mechanism, which gives rise to a significant room-temperature conductivity of 1.03 x 10(-4) S cm(-1) at 70% RH for 1, 4.60 x 10(-6) S cm(-1) at 60% RH for 2, and 3.04 x 10(-5) S cm(-1) at 70% RH for 3.