Uranyl dication mediated photoswitching of a calix[4]pyrrole-based metal coordination cage

Abstract

A set of self-assembled tri- and tetrapodal metal coordination cage structures (cage-1 and cage-2, respectively) constructed from the uranyl dication (UO22+) and a dibenzoic acid functionalised cis-calix[4]pyrrole (1) are described. The inherent photochemical reactivity of the uranyl dication mediates the transformation of cage-1 to cage-2via the activation of molecular oxygen.

Controlled Photocatalytic Hydrocarbon Oxidation by Uranyl Complexes

“…Other reported uranyl‐peroxo oligomers have Raman bands between 820 and 870 cm −1 . This product could be formed as the result of a photolytically‐induced oxygen reduction, something observed very recently in other uranyl complexes derived from photoreactions . Combustion analysis performed on this solid (42.5 % C, 2.7 % H, 6.0 % N) is also consistent with a formulation of [(U VI O 2 ) 2 (μ‐O 2 )(NO 3 ) 2 (Ph 2 phen) 2 ].…”

Chiral Discrete and Polymeric Uranyl Ion Complexes with (1R,3S)-(+)-Camphorate Ligands: Counterion-Dependent Formation of a Hexanuclear Cage

“…connectivity results in the formation of a tetra-nodal 2D assembly parallel to (010), which has the point (Schläfli) symbol {4.6 2 }2{4 2 .6 2 .8 2 }{4 2 .6 3 .8}2{4 2 .6}2 and is represented in Figure 3d. previous examples being either dinuclear (helicate), 36 tetranuclear, 26,[37][38][39] octanuclear, 17,22,23,28,32,34,35 or even of higher nuclearity. 32,35 The [(UO2)6(cam)9] 6moiety in 5…”

“…Cages and metallacycles are still relatively rare in uranyl chemistry, apart from the family of uranyl peroxides, 27 and, in addition to those already mentioned, only about a dozen are known, [28][29][30][31][32][33][34][35][36][37][38][39] most of them containing carboxylate ligands. Reported herein are five uranyl ion complexes synthesized from (1R,3S)-(+)-camphoric acid, three of which include bulky 3d-block metal-containing countercations, and the other two PPh4 + and PPh3Me + cations.…”

Uranyl Ion Complexes of Polycarboxylates: Steps towards Isolated Photoactive Cavities

“…That the estimated internal volume [63] of the cage in B is less than that of the cavity in A may explain why only water molecules are found within and the triethylammonium counter cations are located externally, being involved in H-bonding to peroxo-O atoms. The same limitation to its utility must be applied again to the more recently described cavity-containing complex obtained through reaction of uranyl nitrate with a dicarboxylate derivative of calix [4]pyrrole (cpdc 2− ) to give a product of composition The same limitation to its utility must be applied again to the more recently described cavity-containing complex obtained through reaction of uranyl nitrate with a dicarboxylate derivative of calix [4]pyrrole (cpdc 2− ) to give a product of composition [(UO 2 ) 4 (cpdc) 4 (O 2 ) 2 ](pyH) 4 •4dmf, (C, CSD refcode IDOKIY; dmf = dimethylformamide) ( Figure 3) [65]. Interestingly, the capsular form of the [(UO 2 ) 4 (cpdc) 4 (O 2 ) 2 ] 4− anion present cannot here be attributed to the convergent nature of the U(O 2 )U units, since these are not centred on a common point, and must instead be a consequence of the convergent array of the carboxylate substituents of cpdc 2− .…”

“…Chemistry 2020, 2, 63-79 66 [(UO2)4(cpdc)4(O2)2](pyH)4⋅4dmf, (C, CSD refcode IDOKIY; dmf = dimethylformamide) ( Figure 3) [65]. Interestingly, the capsular form of the [(UO2)4(cpdc)4(O2)2] 4− anion present cannot here be attributed to the convergent nature of the U(O2)U units, since these are not centred on a common point, and must instead be a consequence of the convergent array of the carboxylate substituents of cpdc 2− .…”