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

Hisashi O Kawa; Yukihiro Yoshida; Kazuya Otsubo; Hiroshi Kitagawa

doi:10.1021/acs.inorgchem.9b02861

Network-Selectivity, Magnetism, and Proton Conduction of 2-D and 3-D Metal-Organic Frameworks of the Constituents {P(CH₂OH)₄}⁺/M^II (Mn^II, Fe^II, or Co^II)/[Cr^III(ox)₃]³

Inorg Chem. 2020 Jan 6;59(1):623-628. doi: 10.1021/acs.inorgchem.9b02861. Epub 2019 Dec 10.

Authors

Hisashi O Kawa^{1

2}, Yukihiro Yoshida³, Kazuya Otsubo³, Hiroshi Kitagawa^{3

2}

Affiliations

¹ Department of Chemistry, Graduate School of Science , Kyushu University , 744 Motooka , Nishi-ku, Fukuoka 819-0395 , Japan.
² JST-CREST , Gobancho 7 , Chiyoda-ku, Tokyo 102-0076 , Japan.
³ Division of Chemistry, Graduate School of Science , Kyoto University , Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502 , Japan.

PMID: 31820969
DOI: 10.1021/acs.inorgchem.9b02861

Abstract

Two types of metal-organic frameworks (MOFs), including {P(CH₂OH)₄}₆[Mn^II₃{Cr^III(ox)₃}₄]·10H₂O·2EtOH (1) and {P(CH₂OH)₄}[M^IICr^III(ox)₃]·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, [Mn₃{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 × 10^-4 S cm^-1 at 70% RH for 1, 4.60 × 10^-6 S cm^-1 at 60% RH for 2, and 3.04 × 10^-5 S cm^-1 at 70% RH for 3.