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Porphyrinylphosphonate‐Based Metal–Organic Framework: Tuning Proton Conductivity by Ligand Design
Author(s) -
Yu. Enakieva Yulia,
Sinelshchikova Anna A.,
Grigoriev Mikhail S.,
Chernyshev Vladimir V.,
Kovalenko Konstantin A.,
Stenina Irina A.,
Yaroslavtsev Andrey B.,
Gorbunova Yulia G.,
Yu. Tsivadze Aslan
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003893
Subject(s) - conductivity , deprotonation , nickel , proton , ligand (biochemistry) , chemistry , metal , crystallography , relative humidity , inorganic chemistry , organic chemistry , receptor , ion , biochemistry , physics , quantum mechanics , thermodynamics
A novel metal–organic framework [Zn 3 (Ni‐H 2 TPPP)(Ni‐H 4 TPPP)(Ni‐H 5 TPPP) ⋅ 7(CH 3 ) 2 NH 2 ⋅ DMF ⋅ 7 H 2 O] (where Ni‐H x 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.
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