Porphyrinylphosphonate-Based Metal-Organic Framework: Tuning Proton Conductivity by Ligand Design.
Yulia Yu EnakievaAnna A SinelshchikovaMikhail Semenovich GrigorievVladimir V ChernyshevKonstantin Aleksandrovich KovalenkoIrina A SteninaAndrey B YaroslavtsevYulia G GorbunovaAslan Yu TsivadzePublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2020)
A novel metal-organic framework [Zn3 (Ni-H2 TPPP)(Ni-H4 TPPP)(Ni-H5 TPPP)⋅7(CH3 )2 NH2 ⋅DMF⋅7 H2 O] (where Ni-Hx TPPP (x=2,4,5) are partially deprotonated [5,10,15,20-tetrakis(3-(phosphonatophenyl)-porphyrinato(2-))]nickel(II) species), IPCE-2Ni, with outstanding proton conductivity (1.0×10-2 S cm-1 at 75 °C and 95 % relative humidity) has been obtained. The high concentration of free phosphonate groups and compensating dimethylammonium cations bound by hydrogen bonds in the unique crystal structure of IPCE-2Ni is a key factor responsible for the observed high proton conductivity, which is one order of magnitude higher than for the corresponding MOF based on 5,10,15,20-tetrakis(4-(phosphonatophenyl)porphyrinato(2-))]nickel(II) IPCE-1Ni and comparable with that of leaders among MOFs.