The First Family of Actinide Carboxyphosphinates: Two‐ and Three‐Dimensional Uranyl Coordination Polymers

Abstract

Reaction of uranyl dications with (2-carboxyethyl)(phenyl)-phosphinic acid (CPPA, H 2 L) under hydrothermal conditions gave two layered isomers (UO 2 ) 2 (L) 2 , namely, CPP-U1 and CPP-U2. Both of them feature edge-sharing uranyl dimers as structure-building units, which are ligated by CPP ligands in different ways, thus leading different layered arrangements. With the addition of imidazole derivatives, two three-dimensional structures UO 2 (L)(dib) 0.5 (CPP-U3) and UO 2 (L)(bbi) 0.5

Phosphinic Acid Based Linkers: Building Blocks in Metal–Organic Framework Chemistry

“…[12] One possible strategy for the preparation of water-stable MOFs is to use linker groups that form very strong bonds with tri-and tetravalent cations.I nt his context, linkers based on diaryl or dialkylphosphinates (with the general formula R 2 POOH) show promise as they can form coordination architectures similar to those of carboxylates,and yet do so,in accordance with hard and soft acid and base (HSAB) theory, with stronger bonds to hard metals like Fe III and Zr IV .Perhaps then surprisingly,p hosphinates have obtained much less attention for the preparation of coordination polymers, [13] especially in comparison with carboxylic acid based linkers. [2] Until now only monophosphinic acids, [14][15][16] bisphosphinic acids with as hort spacer, [17,18] or bisphosphinic acids with af lexible spacer [19] have been used for the preparation of coordination polymers ( Figure 1). None of these linkers, however, produced coordination polymers displaying permanent porosity.…”

Unprecedented Catalytic Behavior of Uranyl(VI) Compounds in Chemical Reactions

“…In recent years, uranyl coordination polymers and uranyl‐organic frameworks have received enormous attention owing to their intriguing structural diversities as well as possessing the ability to use sunlight. [ 76–78 ] Their structural diversities exhibit many interesting photochemical properties such as photoluminescence, photocurrent, photocatalysis, etc. Generally, the UO 2 2+ ion is very stable and enjoys a stretchy coordination environment of bipyramidal polyhedra with six to eight donor atoms.…”

“…[79] Performances of some uranyl coordination polymers and frameworks toward the degradation of various organic molecular systems are summarized in Table 1. [78][79][80][81][82][83][84][85][86][87]…”

Phosphinic Acid Based Linkers: Building Blocks in Metal–Organic Framework Chemistry

“…Perhaps then surprisingly, phosphinates have obtained much less attention for the preparation of coordination polymers, especially in comparison with carboxylic acid based linkers . Until now only monophosphinic acids, bisphosphinic acids with a short spacer, or bisphosphinic acids with a flexible spacer have been used for the preparation of coordination polymers (Figure ). None of these linkers, however, produced coordination polymers displaying permanent porosity.…”