Tuning the iron redox state inside a microporous porphyrinic metal organic framework

被引：14

作者：

Abeykoon, Brian ^{[1
]}

Greneche, Jean-Marc ^{[2
]}

Jeanneau, Erwann ^{[1
]}

Chernyshov, Dmitry ^{[3
]}

Goutaudier, Christelle ^{[1
]}

Demessence, Aude ^{[4
]}

Devic, Thomas ^{[5
,6
]}

Fateeva, Alexandra ^{[1
]}

机构：

[1] Univ Claude Bernard Lyon 1, Univ Lyon, Lab Multimat & Interfaces, CNRS,UMR 5615, F-69622 Villeurbanne, France

[2] Univ Maine, CNRS, UMR 6283, Inst Mol & Mat Mans, Ave Olivier Messiaen, F-72085 Le Mans, France

[3] Swiss Norwegian Beamline, ESRF BP 220, F-38043 Grenoble, France

[4] Univ Claude Bernard Lyon 1, Inst Rech Catalyse & Environm Lyon, CNRS, UMR 5256, Villeurbanne, France

[5] Univ Versailles St Quentin En Yvelines, CNRS, UMR 8180, Inst Lavoisier, 45 Ave Etats Unis, F-78035 Versailles, France

[6] Inst Mat Nantes, 2 Rue Houssiniere,BP32229, F-44322 Nantes 3, France

来源：

DALTON TRANSACTIONS | 2017年 / 46卷 / 02期

关键词：

MIXED-VALENCE; THIN-FILMS; HETEROGENEOUS CATALYSTS; HYDROGEN STORAGE; CHARGE-TRANSFER; ADSORPTION; SEPARATION; MOSSBAUER; REDUCTION; SORPTION;

D O I：

10.1039/c6dt04208b

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Two new 3D porphyrin-based metal organic frameworks were obtained by solvothermally reacting iron(III) chloride, a free base (5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl) phenyl] porphyrin) (H2TTPP) and either pyrazine or 1,4-diazabicyclo[2.2.2] octane (DABCO). Both MOFs displayed a 3-D open framework of the fry topology, where the inorganic building unit is a chain of corner-sharing FeN4O2 octahedra and the porphyrinic linker is metallated with iron during the reaction course, with the N-donor base bridging the iron of the porphyrinic cores. Through thorough structural and spectroscopic analyses of the pyrazine containing material the chemical formula [Fe(II)pzTTP(Fe-1-x(II) (DMF1-xFexOHx)-O-III)](n) was inferred (x >= 0.25). Whereas the already reported carboxylate analogue is built up from a pure iron(III) inorganic chain, here spectroscopic and structural studies evidenced a mixed valence iron(II/III) state, evidencing that, in agreement with the HSAB theory, the substitution of a carboxylate function by a tetrazolate one allows redox tuning. Finally, both materials feature one-dimensional channels of ca. 8 x 12 angstrom within the structures with permanent microporosity.

引用

页码：517 / 523

页数：7