Time-controlled synthesis of the 3D coordination polymer U(1,2,3-Hbtc)₂ followed by the formation of molecular poly-oxo cluster {U₁₄} containing hemimellitate uranium(iv)

Abstract

The synthesis of a 3D coordination polymer [U(HL)2] (L = hemimellitate) and a new poly-oxo cluster {U14} afterwards is presented.

Mononuclear to Polynuclear UIV Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation

“…Consistent with this, Loiseau et al. have recently isolated {U 12 } and {U 14 } clusters and proposed that polyoxo clusters may assemble through the condensation of U 6 O 4 (OH) 4 species with dinuclear units such that “6+2 n ” nuclearity units, where n =1–6, may be accessible . Mazzanti and Hixon isolated {An 16 } units for U and Pu, respectively, but these clusters differ significantly from those reported by Loiseau et al.…”

“…Moreover, to the best of our knowledge, a {U 14 } cluster akin to that observed in the U 38 cluster has not been observed for the tetravalent actinides thus far. Though a polyoxo {U 14 } cluster was recently reported, it differs significantly from the core unit in the U 38 cluster . For related Pu 38 clusters, Hixon et al.…”

Metal–Organic Frameworks Based on Group 3 and 4 Metals

“…[43] Besides, An 6 clusters are generally obtained by reacting AnCl 4 and 4-hydroxybenzoic acid in water at room temperature. [44] An(IV)-oxo clusters with other nuclear numbers include An 3 (An = Np, [45] Th [46] ), An 4 (An = Np [45] ), and An 14 (An = U [47] ). Note that only representative MOFs based on group 3 and 4 metals (excluding Sc and Hf) since 2018 and previous MOF milestones are listed; b) Linkers are abbreviated as: ABTC = 3,3′,5,5′-azobenzene-tetracarboxylate; AZDC = azobenzene-3,3′-dicarboxylate; ATDB = 4,4′-(4-amino-4H-1,2,4-triazole-3,5-diyl)-dibenzoate; ATPC = 4′,4′′,4′′′,4′′′′-(anthracene-9,10-diylidenebis(methan-1,1-diyl-1-ylidene))tetrabiphenyl-4-carboxylate; ATBC = 4,4′,4′′,4′′′-(anthracene-9,10-diylidenebis(methan-1,1-diyl-1-ylidene)) tetrabenzoate; BDC = terephthalate; BTTC = benzotristhiophene carboxylate; BHPB = hexakis(4-(4-carboxyphenyl)phenyl)benzoate; BDHA = benzene-1,4-dihydroxamic acid; BDB = 4,4′-(benzene-1,3-diyl)dibenzoate; BTDB = 4,4′-(benzo[c] [1,2,5]thiadiazole-4,7-diyl)dibenzoate; BTBA = 4,4′,4′′-(1H-benzo-[d]imidazole-2,4,7-triyl)tribenzoate; BPDC = biphenyl-4,4′-dicarboxylate; BPyDC = 2,2′-bipyridyl-5,5′-dicarboxylate; BTB = 1,3,5-benzenetrisbenzoate; CPTPY = 4′-(4-carboxyphenyl)-terpyridine; BTB = benzene tribenzoate; CBTB = 4,4′,4′′,4′′′-(9H-carbazole-1,3,6,8-tetrayl)tetrabenzoate; DCDPS = 4,4′-dicarboxydiphenyl sulfone; DTPP = 5,15-di(3,4,5-trihydroxyphenyl)porphyrin; DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid; EDDB = 4,4′-(ethyne-1,2-diyl)dibenzoate; FUM = fumarate; 2,6-NDC = naphthalene-2,6-dicarboxylate; HBCPB = 1,2,3,4,5,6-hexakis[3,5-bis(4-carboxyphenyl)phenoxymethyl]benzene; HCHC = hexakis(4-carboxyphenyl)hexabenzocoronene; H 6 CPB/HCBB = 1′,2′,3′,4′,5′,6′-hexakis(4carboxyphenyl)benzene; H 6 TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid; H 2 DHBQ = 2,5-dihydroxybenzoquinone; INA = isonicotinate; L-AA = L-Aspartic acid; MDIP = 3,3′,5,5′-tetracarboxydiphenylmethane; PDC = 2,5-pyridinedicarboxylate; P-2COOH = N,N′-di-(4-benzoic acid)-1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide; TCPP = meso-tetrakis(4-carboxylatephenyl)porphyrin; TTFTB = tetrathiafulvalene-tetrabenzoate; TDHT = 2,4,6-tri(3,4-dihydroxyphenyl)-1,3,5triazine; TCPC = 5,10,15-tris(p-carboxylphenyl)corrole; TBAPY = 1,3,6,8-tetrakis(p-benzoic acid)pyrene; TTFTB = tetrathiafulvalene tetrabenzoate; TPHB = 4,4′,4′′,4′′′,4′′′′,4′′′′-(triphenylene-2,3,6,7,10,11-hexayl)hexabenzoate; THPP = 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin); THBPP = 5,10,15,20-tetrakis(3,4,5-trihydroxybiphenyl)porphyrin; TPDC = 2′,5′-dimethyl-terphenyl-4,4′′-dicarboxylate; TTDA = 5′-(1H-tetrazol-5-yl)-1,1′:3′,1′′-terphenyl-4,4′′-dicarboxylate; TBCPB = 1,2,4,5-tetrakis [ Ti-oxo clusters are widely considered as a TiO 2 nanomaterial at a molecular level, and receive considerable attention due to their structural diversity as well as potential applications in catalysis, biomedicine and environments.…”

“…[ 43 ] Besides, An 6 clusters are generally obtained by reacting AnCl 4 and 4‐hydroxybenzoic acid in water at room temperature. [ 44 ] An(IV)‐oxo clusters with other nuclear numbers include An 3 (An = Np, [ 45 ] Th [ 46 ] ), An 4 (An = Np [ 45 ] ), and An 14 (An = U [ 47 ] ).…”

Snapshots of Ce70 Toroid Assembly from Solids and Solution

“…Of special note, Zr/Hf MOFs are built of the M6(OH,O)8 hexamer (M6), and these MOFs are widely exploited for virtually every application that has been developed to date including catalysis and separations. 37 The M6 cluster is contained within most M IV -oxoclusters, as well as in fluorite-type MO2; but it is not possible to simply build MO2 (and intermediate size clusters such as M38 [38][39][40][41][42][43][44] ) from M6-units, since the M6-units share M2 edges in the larger assemblies. In fact, M6 is shown to co-exist in solution with monomers, dimers and hexamers, [45][46] likely in dynamic equilibrium.…”