One‐, Two‐, and Three‐Dimensional Coordination Polymers Built from Large Mo 36 ‐Polyoxometalate Anionic Units and Lanthanide Cations

Autor: N. V. Izarova, Dieter Fenske, Vladimir P. Fedin, Dmitrij Yu. Naumov, Denis G. Samsonenko, Maxim N. Sokolov, Alexander Rothenberger
Rok vydání: 2005
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2005:4985-4996
ISSN: 1099-0682
1434-1948
Popis: The Mo 3 6 -Polyoxometalate [Mo 3 6 O 1 0 8 (NO) 4 (H 2 O) b 16] 1 2 - reacts with Ln 3 + to give crystalline solids with 1D, 2D, and 3D polymeric frameworks, depending on the size of Ln 3 + and the reaction conditions. Reaction of LaCl 3 with (NH 4 ) 1 2 -[Mo 3 6 O 1 0 8 (NO) 4 (H 2 O) 1 6 ] gives (H 3 O) 2 [{La(H 2 O) 5 } 2 {La(H 2 O) 6 }-{La(H 2 O) 5 Cl}{Mo 3 6 (NO) 4 O 1 0 8 (H 2 O) 1 6 )}]Cl.21H 2 O (1), in whose structure the La 3 + cations and the polyoxometalate anions are united in a 3D framework, whereas NdCl 3 and SulCl 3 give [{Ln(H 2 O) 6 ) 4 {Ln(H 2 P) 4 }{Mo 3 6 (NO) 4 O 1 0 8 (H 2 O) 1 6 )]-Cl 3 .nH 2 O [Ln = Nd, n = 24 (2); Ln = Sm, n = 21 (3)], which have 2D frameworks. Under different conditions, large Ln 3 + ions (La-Nd) give the one-dimensional coordination polymers [{Ln(H 2 P) 6 } 2 {Ln(H 2 O) 7 } 2 {Mo 3 6 (NO) 4 O 1 0 8 (H 2 O) 1 6 }].nH 2 O [Ln = La, n = 29 (4); Ln = Ce, n = 41 (5), Ln = Pr; n = 40 (6), Ln = Nd, n = 36 (7)], whereas reaction with Gd(NO 3 ) 3 gives [{Gd(H 2 O) 5 ] 4 {Mo 3 6 (NO) 4 O 1 0 8 )(H 2 O) 1 6 }].34H 2 O (8), which has a unique 2D layered structure: Smaller Ln 3 + ions (Tb-Lu) give isostructural 1D chain coordination polymers (H 3 O) 3 -[{Ln(H 2 P) 6 } 2 {Ln(H 2 O) 4 ){Mo 3 6 (NO 4 )O 1 0 8 (H 2 O) 1 6 }].nH 2 O [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 [Mo 3 6 O 1 1 2 -(H 2 O) 1 6 ] 8 - , namely (H 3 O) 2 [{Nd(H 2 O) 5 ) 2 {Mo 3 6 O 1 1 2 (H 2 O) 1 6 }]. 40H 2 O (15), was prepared from MoO 4 2 - , NH 2 OH, 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 Ln 3 + to the oxygen atoms of terminal cis-MoO 2 2 + groups is responsible for the formation of these polymeric frameworks. The coordination numbers of Ln 3 + change from 9 (La-Sm) to 8 (Gd-Lu).
Databáze: OpenAIRE
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