Infinite terbium(iii) chains formed from a tetra-phosphorylated resorcinarene cavitand

Abstract

Reaction of [Tb(III)(DMSO)(8)](CF(3)SO(3))(3) with a resorcinarene cavitand substituted by four -CH(2)P(O)Ph(2) pendant arms afforded an infinite 1D inorganic polymer, in which the consecutive resorcinarene units are linked through two terbium strands, this connection involves pairs of phosphoryl groups occupying adjacent positions of the resorcinarene units.

Lanthanide phosphine oxide complexes

“…The reaction of [Tb(DMSO) 8 ](OTf) 3 with the resorcinarene (71) gives the polymeric complex, [Tb 2 (71)(DMSO) 8 ](OTf) 6 in which [Tb(71)(DMSO) 4 (OTf)] 2+ units are linked in a chain. The terbium ions have a 7-coordiate pentagonal bipyramidal arrangement comprising two PO groups in axial positions with the equatorial plane made up of one OTf À and four DMSO [144]. Analysis of the luminescence spectra indicates that there is no electronic interaction between the two terbium centres in the polymer.…”

Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes

“…There was no evidence of shortened An−O (TPPO) bonds caused by the actinide contraction across the series. Other phosphine oxide complexes reported were [UO 2 {(Ph) 2 P(O)-CH 2 Cl} 2 (NO 3 ) 2 ], 47 [NpO 2 (DPPMO 2 ) 2 Cl] 2 [NpO 2 Cl 4 ] (in which the phosphine oxide ligands are bidentate) (9), 48 [NpO 2 (phosox 1 )(EtOH)(NO 3 )] n , 49 [UO 2 (phosox 2 )Cl 2 ] (a second molecule in the crystal structure was either the same U(VI) complex or a U(V) complex of formula [UOCl 3 L] with 0.5:0.5 occupancy), 50 and [UO 2 (NO 3 ) 2 (DPPFO 2 )] in which DPPFO 2 is bis(diphenylphosphino ferrocene) dioxide, a bifunctional phosphine oxide added to the reaction solution as a dihydrate. 51 A number of bifunctional neutral oxygen donors have attracted interest because they have exhibited promising felement separation properties in solvent-extraction studies.…”

Resorcinarene-based cavitands as building blocks for crystal engineering

“…4). 44 More complex bilayer structures constructed from secondary building units were obtained using a flexible cavitand modified at the lower rim with four carboxylic groups. By mixing a tetraIJphosphineoxide) cavitand with [TbIJDMSO) 8 ](CF 3 SO 3 ) 3 , an infinite 1-D polymer was also synthetized (UTAVOB, Fig.…”

“…2). 27 The generation of new architectures with one or more cavitands connected through a metal centre has been realized by synthetizing cavitands decorated both at the upper rim 28a,b and at the lower rim 28c with groups suitable for metal complexation (see for instance OCIWAY, 29 AQEQAP, 30 JOZUG and JOZLAN, 31 Fig. 2).…”

“…4) by Toupet and coworkers in 2011, showing consecutive cavitand units linked through two terbium ions, adopting a rare pentagonal bipyramidal coordination geometry. 44 More complex bilayer structures constructed from secondary building units were obtained using a flexible cavitand modified at the lower rim with four carboxylic groups. Different metal centres were used to assemble other types of coordination polymers, namely, cadmium (COKFUF, Fig.…”