Zinc 4-Carboxyphenylphosphonates with Pillared Layered Framework Structures Containing Large 12-Membered Rings Built Up from Tetranuclear Zn₄ Clusters and CPO₃ Linkages

Abstract

Twoisostructuralzincphosphonates[Zn(H 2 O) 6 ][Zn 8 (OOCC 6 H 4 PO 3 ) 6 (4,4′-bipy)](1)and(dabcoH) 2 [Zn 8 (OOCC 6 H 4 PO 3 ) 6 ] • 6H 2 O (2) (dabco ) 1,4-diazabicyclo[2.2.2]octane) have been obtained by hydrothermal reactions of zinc sulfate and 4-carboxyphenylphosphonic acid in the presence of additional organic ligands 4,4′-bipyridine and 1,4-diazabicyclo[2.2.2]octane, respectively. Both show pillared layered open framework structures. The inorganic layers are of particular interest in which the highly symmetric tetranuclear clusters, composed of corner-sharing {ZnO 4 } and {ZnO 3 N} tetrahedra, are linked by {CPO 3 } tetrahedra through cornersharing, forming an inorganic layer containing large 12-membered windows. The [Zn(H 2 O) 6 ] 2+ cations (for 1) or lattice water (for 2) reside in the cavities generated by the 12-membered windows and the organic pillars.

Phosphonate and sulfonate metal organic frameworks

“…[49][50][51][52] A new functional group on the organophosphonate ligand would perturb the layered structure in metal diphosphonates with the result hopefully being a new 3-D open framework. The functional groups attached to the phosphonic acid to create 3-D open frameworks have included imino, 51 hydroxyl 53 carboxylic acid 54,55 sulfonic acid [56][57][58] and pyridine. 37,59 This is a large field where many structurally characterized products with infinite metal ligand connectivity have formed dense solids.…”

Three-dimensional metal phosphonodicarboxylates with GIS-zeolite topology: syntheses, structures and magnetic studies

“…15 By using the same ligand, we reported two isostructural zinc phosphonocarboxylates [Zn(H 2 O) 6 ][Zn 8 (4-OOCC 6 H 4 PO 3 ) 6 (4,4¢bipy)] and (dabcoH) 2 [Zn 8 (4-OOCC 6 H 4 PO 3 ) 6 ]•6H 2 O (dabco = 1,4-diazabicyclo[2.2.2]octane) with pillared layered structures. 16 The inorganic layers contain large 12-membered windows made up of symmetric tetranuclear Zn 4 clusters and {PO 3 C} linkages.…”

LiF-assisted crystallization of zinc 4-carboxyphenylphosphonates with pillared layered structures

“…The layer topologies are remarkably different from those in the related zinc 4-carboxyphenylphosphonate compounds which were obtained by using organic amines as structure-directing agents. 13,14 For example, compounds [Zn(H 2 O) 6 ][Zn 8 (OOCC 6 H 4 PO 3 ) 6 (4,4 0 -bipy)] and (dabcoH) 2 [Zn 8 (OOCC 6 H 4 PO 3 ) 6 ]$6H 2 O (dabco ¼ 1,4-diazabicyclo[2.2.2]octane) contain inorganic layers made up of highly symmetric tetranuclear clusters of Zn 4 and {CPO 3 } tetrahedra through corner-sharing, 13 while in the pillared layered compounds Zn 4 (OOCC 6 H 4 PO 3 ) 3 $HTEA, Zn 3 (OOCC 6 H 4 PO 3 ) 2 (en) 2 and Zn 3 (OOCC 6 H 4 PO 3 ) 2 (H 2 O) (TEA ¼ triethylamine, en ¼ ethylenediamine), the Zn-O-P inorganic layers containing 4-, 16-member rings, 3-, 4-, 12-member rings, and 3-, 8-member rings are found. 14…”