One-, two-, and three-dimensional coordination polymers built from large Mo36-polyoxometalate anionic units and lanthanide cations

Natalia V. Izarova, Maxim N. Sokolov, Denis G. Samsonenko, Alexander Rothenberger, Dmitrij Yu Naumov, Dieter Fenske, Vladimir P. Fedin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

The Mo36-polyoxometalate [Mo36O108(NO) 4(H2O)16]12- reacts with Ln 3+ to give crystalline solids with 1D, 2D, and 3D polymeric frameworks, depending on the size of Ln3+ and the reaction conditions. Reaction of LaCl3 with (NH4) 12-[Mo36O108(NO)4(H 2O)16] gives (H3O)2[{La(H 2O)5}2{La(H2O)6}- {La(H2O)5Cl}{Mo36(NO)4O 108(H2O)16}]Cl·21H2O (1), in whose structure the La3+ cations and the polyoxometalate anions are united in a 3D framework, whereas NdCl3 and SmCl3 give [{Ln(H2O)6}4{Ln(H2O) 4}{Mo36(NO)4O108(H 2O)16}]-Cl3·nH2O [Ln = Nd, n = 24 (2); Ln = Sm, n = 21 (3)], which have 2D frameworks. Under different conditions, large Ln3+ ions (La-Nd) give the one-dimensional coordination polymers [{Ln(H2O)6}2{Ln(H2O) 7}2{Mo36(NO)4O108(H 2O)16}]·nH2O [Ln = La, n = 29 (4); Ln = Ce, n = 41 (5), Ln = Pr; n = 40 (6), Ln = Nd, n = 36 (7)], whereas reaction with Gd(NO3)3 gives [{Gd(H2O)5} 4{Mo36(NO)4O108(H2O) 16}]·34H2O (8), which has a unique 2D layered structure. Smaller Ln3+ ions (Tb-Lu) give isostructural 1D chain coordination polymers (H3O)3-[{Ln(H2O) 6}2{Ln(H2O)4}{Mo36(NO) 4O108(H2O)16}]·nH 2O [Ln = Tb, n = 42 (9); Ln = Dy, n = 43 (10), Ln = Ho, n = 46 (11), Ln = Er, n = 50 (12); Ln = Yb, n = 56 (13); Ln = Lu, n = 31 (14)]. The first coordination polymer based on [Mo36O112-(H 2O)16]8-, namely (H3O) 2[{Nd(H2O)5}2{Mo36O 112(H2O)16}]· 40H2O (15), was prepared from MoO42-, NH2OH, and Nd 3+. It has a 2D layered structure. All these compounds are obtained in moderate to high yields (35-93 %), and were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray structural analysis. Direct coordination of Ln3+ to the oxygen atoms of terminal cis-MoO 22+ groups is responsible for the formation of these polymeric frameworks. The coordination numbers of Ln3+ change from 9 (La-Sm) to 8 (Gd-Lu).

Original languageEnglish (US)
Pages (from-to)4985-4996
Number of pages12
JournalEuropean Journal of Inorganic Chemistry
Issue number24
DOIs
StatePublished - Dec 16 2005

Keywords

  • Coordination polymers
  • Lanthanides
  • Molybdenum
  • Polyoxometalates

ASJC Scopus subject areas

  • Inorganic Chemistry

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