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

doi:10.1002/ejic.200500484

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 journal › Article › peer-review

35 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 MoO₄^2-, 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 language	English (US)
Pages (from-to)	4985-4996
Number of pages	12
Journal	European Journal of Inorganic Chemistry
Issue number	24
DOIs	https://doi.org/10.1002/ejic.200500484
State	Published - Dec 16 2005
Externally published	Yes

Keywords

Coordination polymers
Lanthanides
Molybdenum
Polyoxometalates

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.200500484

Cite this

@article{3e6134027a3244749ef053dba285d2f2,

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

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).",

keywords = "Coordination polymers, Lanthanides, Molybdenum, Polyoxometalates",

author = "Izarova, {Natalia V.} and Sokolov, {Maxim N.} and Samsonenko, {Denis G.} and Alexander Rothenberger and Naumov, {Dmitrij Yu} and Dieter Fenske and Fedin, {Vladimir P.}",

year = "2005",

month = dec,

day = "16",

doi = "10.1002/ejic.200500484",

language = "English (US)",

pages = "4985--4996",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "24",

}

TY - JOUR

T1 - One-, two-, and three-dimensional coordination polymers built from large Mo36-polyoxometalate anionic units and lanthanide cations

AU - Izarova, Natalia V.

AU - Sokolov, Maxim N.

AU - Samsonenko, Denis G.

AU - Rothenberger, Alexander

AU - Naumov, Dmitrij Yu

AU - Fenske, Dieter

AU - Fedin, Vladimir P.

PY - 2005/12/16

Y1 - 2005/12/16

N2 - 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).

AB - 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).

KW - Coordination polymers

KW - Lanthanides

KW - Molybdenum

KW - Polyoxometalates

UR - http://www.scopus.com/inward/record.url?scp=29344463824&partnerID=8YFLogxK

U2 - 10.1002/ejic.200500484

DO - 10.1002/ejic.200500484

M3 - Article

AN - SCOPUS:29344463824

SN - 1434-1948

SP - 4985

EP - 4996

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 24

ER -