Lanthanide N,N'-piperazine-bis(methylenephosphonates) (Ln=La, Ce, Nd) that display flexible frameworks, reversible hydration and cation exchange

Journal Article · Thu Oct 15 00:00:00 EDT 2009 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.07.019· OSTI ID:21372344

Mowat, John P.S.; Groves, John A; Wharmby, Michael T; Miller, Stuart R; Yang, Li; Lightfoot, Philip ^[1]

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1. School of Chemistry, University of St. Andrews, Purdie Building, North Haugh, St. Andrews, Fife KY16 9ST (United Kingdom)

Hydrothermal syntheses of lanthanide bisphosphonate metal organic frameworks comprising the light lanthanides lanthanum, cerium and neodymium and N,N'-piperazine bis(methylenephosphonic acid) (H{sub 2}L(1) and its 2-methyl and 2,5-dimethyl derivatives (H{sub 2}L(2) and H{sub 2}L(3)) gives three new structure types. At elevated starting pH (ca. 5 and above) syntheses give 'type I' materials with all metals and acids of the study (MLnLxH{sub 2}O, M=Na, K, Cs; Ln=La, Ce, Nd; x{approx}4: KCeL(1).4H{sub 2}O, C2/c, a=23.5864(2) A, b=12.1186(2) A, c=5.6613(2) A, beta=93.040(2){sup o}). The framework of structure type I shows considerable flexibility as the ligand is changed, due mainly to rotation around the -N-CH{sub 2}- bond of the linker in response to steric considerations. Type I materials demonstrate cation exchange and dehydration and rehydration behaviour. Upon dehydration of KCeL.4H{sub 2}O, the space group changes to P2{sub 1}/n, a=21.8361(12) A, b=9.3519(4) A, c=5.5629(3) A, beta=96.560(4){sup o}, as a result of a change of the piperazine ring from chair to boat configuration. When syntheses are performed at lower pH, two other structure types crystallise. With the 'non-methyl' ligand 1, type II materials result (LnL(1)H{sub 2}L(1).4.5H{sub 2}O: Ln=La, P-1, a=5.7630(13) A, b=10.213(2) A, c=11.649(2) A, alpha=84.242(2){sup o}, beta=89.051(2){sup o}, gamma=82.876(2){sup o}) in which one half of the ligands coordinate via the piperazine nitrogen atoms. With the 2-methyl ligand, structure type III crystallises (LnHL(2).4H{sub 2}O: Ln=Nd, Ce, P2{sub 1}/c, a=5.7540(9) A, b=14.1259(18) A, c=21.156(5) A, beta=90.14(2){sup o}) due to unfavourable steric interactions of the methyl group in structure type II. - Graphical abstract: The lanthanides La, Ce and Nd give a family of metal organic frameworks based on N,N'-piperazinebismethylenephosphonate ligands: these display reversible dehydration, structural flexibility and cation exchange.

• OSTI ID: 21372344
• Journal Information: Journal of Solid State Chemistry, Vol. 182, Issue 10; Other Information: DOI: 10.1016/j.jssc.2009.07.019; PII: S0022-4596(09)00321-1; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CERIUM COMPLEXES
DEHYDRATION
FLEXIBILITY
HYDROTHERMAL SYNTHESIS
ION EXCHANGE
LANTHANUM COMPLEXES
LIGANDS
MONOCLINIC LATTICES
NEODYMIUM COMPLEXES
PIPERAZINES
SPACE GROUPS
AZINES
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
HETEROCYCLIC COMPOUNDS
MECHANICAL PROPERTIES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRAZINES
RARE EARTH COMPLEXES
SYMMETRY GROUPS
SYNTHESIS
TENSILE PROPERTIES