Solid-state coordination chemistry: Influences of {M(terpyridyl)} (M = Fe(III), Cu(II), Ni(II)} subunits on molybdenum oxide structures

P. J. Hagrman, Jon A Zubieta

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Abstract

The hydrothermal reactions of Na2MoO4·2H2O and 2,2':6',2'-terpyridine with appropriate salts of Fe(II), C]u(II), and ZN(II) yield a variety of mixed metal oxide phases. The Cu(II) system affords the molecular cluster [Cu(terpy)MoO4]·3H2O (MOXI-40·3H2O), as well as a one-dimensional material [Cu(terpy)Mo2O7](MOXI-41) which is constructed from {Mo4O14}4- clusters linked through {Cu(terpy)}2+ units. In contrast, the Zn(II) phase of stoichiometry identical to that of MOXI-41, [Zn(terpy)Mo2O7](MOXI-42), exhibits a one-dimensional structure characterized by a {Mo2O7}(n)(2n-) chain decorated with peripheral {Zn(terpy)}2+ subunits. The iron species [{Fe(terpy)}2Mo4O12](MOXI-43) is also one-dimensional but exhibits [{Fe(terpy)]2{MoO4}2]2+ rings linked through {MoO4}2- tetrahedra. A persistent structural motif which appears in MOXI-40, MOXI-41, and MOXI-43 is the [{M(terpy)}2{MoO4}2](n) cluster with a cyclic {M2Mo2O4} core. In general, the secondary metal sites M(II, III) are effective bridging groups between molybdate subunits of varying degrees of aggregation. Furthermore, the ligands passivate the bimetallic oxide from spatial extension in two or three dimensions and provide a routine entree into low-dimensional structural types of the molybdenum oxide family of materials.

Original languageEnglish (US)
Pages (from-to)5218-5224
Number of pages7
JournalInorganic Chemistry
Volume39
Issue number23
DOIs
StatePublished - Nov 13 2000

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ASJC Scopus subject areas

  • Inorganic Chemistry

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