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Constructing Terbium Co‐ordination Polymers of 4,4′‐Bipyridine‐ N , N ′‐dioxide by Means of Diffusion Solvent Mixtures
Author(s) -
Long DeLiang,
Blake Alexander J.,
Champness Neil R.,
Wilson Claire,
Schröder Martin
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020503)8:9<2026::aid-chem2026>3.0.co;2-8
Subject(s) - terbium , molecule , stoichiometry , chemistry , crystallography , solvent , polymer , hydrogen bond , inorganic chemistry , materials science , organic chemistry , ion
Five different co‐ordination polymers of terbium( III ) and the bidentate ligand 4,4′‐bipyridine‐ N , N ′‐dioxide (L), [Tb(L)(CH 3 OH)(NO 3 ) 3 ] ∞ ( 1 ), {[Tb(L) 1.5 (NO 3 ) 3 ]⋅CH 2 Cl 2 } ∞ ( 2 ), {[Tb(L) 1.5 (NO 3 ) 3 ]⋅CH 3 OH⋅0.8H 2 O} ∞ ( 3 ), {[Tb(L) 1.5 (NO 3 ) 3 ]⋅0.4C 2 Cl 4 ⋅0.8CH 3 OH} ∞ ( 4 ), and [Tb(L) 2 (NO 3 ) 3 ] ∞ ( 5 ) have been synthesised by the use of different “diffusion solvent mixtures”, and structurally characterised by X‐ray crystallography. Compound 1 , with a Tb:L stoichiometry of 1:1, adopts a zig‐zag chain structure, which forms three‐fold interpenetrating diamondoid frameworks through interchain hydrogen bonding between co‐ordinated methanol and a nitrate group on an adjacent chain. Polymers 2, 3 , and 4 all have a Tb:L stoichiometry of 1:1.5, but adopt different topologies. For 2 , a ladder arrangement is found and large channels which accommodate solvent CH 2 Cl 2 molecules are formed by superposition of the ladders. For 3 and 4 4.8 2 net structures are observed. The superposition of the 4.8 2 nets in 3 and 4 , by disposing adjacent layers such that every octagon is positioned below a tetragon from the neighbouring layer, allows the formation of two kinds of channel, with that inside the tetragons accommodating methanol molecules. The other kind of channel, between tetragons, accommodates water molecules in the case of 3 and tetrachloroethylene molecules in the case of 4 . Compound 5 , with a Tb:L stoichiometry of 1:2, has a linear polymeric structure with one bridging and one terminal ligand, and forms (6,3) plane nets by means of intermolecular electrostatic interactions between N ‐oxide moieties. X‐ray powder diffraction studies show that upon desolvation, compound 2 maintains its original ladder framework.