Assembly of a family 12 supramolecular compounds containing [AnO2Cl4]2– (An = U, Np, Pu), via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X H, Cl, Br, I), is reported. These materials were prepared from room-temperature synthesis wherein crystallization unhydrolyzed valence-pure [An(VI)O2Cl4]2– Pu) tectons the norm. We present hierarchy assembly criteria based on crystallographic observations subsequently quantify strengths non-covalent interactions using...

Abstract Spectator ions have known and emerging roles in aqueous metal‐cation chemistry, respectively directing solubility, speciation, reactivity. Here, we isolate structurally characterize the last two metastable members of alkali uranyl triperoxide series, Rb + Cs salts (Cs‐ U 1 Rb‐ ). We document their rapid solution polymerization via small‐angle X‐ray scattering, which is compared to more stable Li , Na K analogues. To understand role alkalis, also quantify alkali‐hydroxide promoted...

Engaging the nominally terminal oxo atoms of linear uranyl (UO22+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within field actinide hybrid materials. An approach has been developed for promoting atom participation range interactions, through judicious choice electron donating equatorial ligands appropriately polarizable halogen-donor atoms. As such, family materials was generated based on combination 2,5-dihalobenzoic acid aromatic, chelating...

The synthesis and crystal structures of eight compounds containing the anionic uranyl isothiocyanate tecton [UO2(NCS)4(H2O)]2−, charge balanced by substituted pyridinium cations (4XpyH: X = Cl, Br, I, SCN, CH3, NH2, N(CH3)2) are reported. Hydrogen bonding interactions between coordinated water molecules non-coordinated sulfur atoms (O–H2⋯S) adjoining tectons facilitate formation infinite 'pseudo' chains inorganic tectons. were paired with these fixed due to their ability sustain multiple...

A novel actinide-containing coordination polymer, [Am(C2O4)(H2O)3Cl] (Am-1), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional comprised of pseudo-dimeric Am3+ nodes are bridged by oxalate ligands to form sheets. Each metal center nine-coordinate, forming a distorted capped square antiprism geometry with C1 symmetry, features bound oxalate, aqua, chloro ligands. Am3+-ligand bonds were probed computationally using...

Postsynthetic modification (PSM) in metal–organic frameworks (MOFs) can introduce multiple functionalities and alter the structural function for desired application. However, PSM of coordination site faces challenges collapse or incompatibility between original metal newly formed group. Herein, we developed a novel concept introducing "primary" "secondary" nodes, coexisting water-stable, Zr-based heterometallic MOF, [Zr6(μ3-OH)8(OH)8][Cu4I(L1)4]2 (1-SH-a, H2L1 =...

Abstract Hybrid materials bearing elements from the 5f block display a rich diversity of coordination geometries, connectivities, and assembly motifs. Exemplary in this regard have been uranyl polymers, which feature wide range secondary building units resulting hydrolysis oligomerization [UO 2 ] 2+ cation. An alternative approach to novel materials, however, suppresses relies on non‐covalent interactions (e.g. hydrogen or halogen bonding) direct more limited suite species units. This may be...

A series of eighteen tetravalent actinide (An = Th, U, Pu) compounds were synthesized from acidic aqueous solutions containing thorium, uranium, or plutonium and a protonated nitrogen heterocycles. The characterized using Raman, IR, optical absorption spectroscopies. structures determined single-crystal X-ray diffraction found to consist [An(H2O)xCly]4–y (x 4–7 y 2–4) AnCl62– molecular units. Breaks in the structural chemistry early actinides observed, with Th adopting exclusively...

The synthesis, structure, and spectroscopic characterization of the first transplutonium metal-organic framework (MOF) is described. preparation structure Am-GWMOF-6, [Am2 (C6 H8 O4 )3 (H2 O)2 ][(C10 N2 )], analogous to that isostructural trivalent lanthanide-only containing material GWMOF-6. presented MOF architecture used as a platform probe Am3+ coordination chemistry guest-enhanced luminescent emission, whereas itself provides means monitor effects self-irradiation upon crystallinity...

The crystal structures of americium species containing a common multifunctional phosphine oxide ligand, reported for its ability to extract f elements from acidic solutions, namely, 2,6-[Ph2P(O)CH2]2C5H3-NO, L, were finally determined after over three decades separations studies involving these and their surrogates. molecular compounds Am(L)(NO3)3, Am 1:1, [Am(L)2(NO3)][2(NO3)], 2:1, along with neodymium europium analogues, synthesized characterized using single-crystal X-ray...

The synthesis and structural characterization of seven new [UO2(NCS)5]3-- [UO2(NCS)4Cl]3--containing materials charge balanced by 4-phenylpyridinium or 4,4'-bipyridinium cations are reported. Assembly these occurs via a diverse set noncovalent interactions, with the most prevalent involving terminal sulfur atoms, which can both accept hydrogen bonds and/or form S···S S···Oyl interactions. electrostatic potential [UO2(NCS)5]3- [UO2(NCS)4Cl]3- anions was calculated mapped on 0.001 au...

Abstract A new uranyl containing metal–organic framework, RPL‐1 : [(UO 2 ) (C 28 H 18 O 8 )] . (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid‐state photoluminescence properties explored. Single crystal X‐ray diffraction data reveals structure of RPL ‐ 1 consists two crystallographically unique three dimensional, interpenetrating nets with a 4,3‐connected tbo topology. Each net contains large pores an average width 22.8 Å is formed from...

Electric field gradient (EFG) tensors in the equatorial plane of linear UO22+ ion have been measured by nuclear magnetic resonance (NMR) and quadrupole (NQR) experiments computed relativistic Kohn-Sham methods with without environment embedding for Cs2UO2Cl4 Cs2UO2Br4. This approach expands possibilities probing electronic structure uranyl complexes beyond strongly covalent U-O bonds. The combined analyses find that one two largest principal EFG tensor components at halogen sites points...

Two lanthanide-containing porous coordination polymers, [Ln2(bpdc)6(phen)2]·nH2O (1) and [Ln2(bpdc)6(terpy)2]·3H2O (2) (Ln = Pr, Nd, or Sm–Dy; bpdc: 2,2′-bipyridine-5,5′-dicarboxylic acid; phen: 1,10-phenanthroline; terpy: 2,2′:6′,2″-terpyridine), have been hydrothermally synthesized structurally characterized by powder single-crystal X-ray diffraction. Crystallographic analyses reveal that compounds 1 2 feature Ln3+-containing dimeric nodes form a two-dimensional (2D) nonporous...

Crystals of a hydrated Pu(iii) chloride, (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O, were grown via slow evaporation from acidic aqueous, high chloride media. X-ray diffraction data reveals the neutral [PuCl3(H2O)5] tecton is assembled charge assisted hydrogen and halogen bonds donated by 4-bromopyridinium cations series inter-tecton bonds.

Four novel Pu(<sc>iv</sc>) nitrato chloro complexes were crystallographically characterized and the Pu–ligand bond nature was delineated computationally.

We report the structural, vibrational, and optical properties of americium formate (Am(CHO

Reported is the synthesis, crystal structure, and solid-state characterization of a new americium containing metal-organic framework (MOF), [Am(C9H3O6)(H2O)], MOF-76(Am). This material constructed from Am3+ metal centers 1,3,5-tricarboxylic acid (BTC) ligands, forming porous three-dimensional that isostructural with several known trivalent lanthanide (Ln) analogs (e.g., Ce, Nd, Sm-Lu). The ions have seven coordinates assume distorted, capped trigonal prismatic geometry C1 symmetry. Am3+-O...

Abstract The synthesis, structure, and spectroscopic characterization of the first transplutonium metal–organic framework (MOF) is described. preparation structure Am‐GWMOF‐6, [Am 2 (C 6 H 8 O 4 ) 3 (H O) ][(C 10 N )], analogous to that isostructural trivalent lanthanide‐only containing material GWMOF‐6. presented MOF architecture used as a platform probe Am 3+ coordination chemistry guest‐enhanced luminescent emission, whereas itself provides means monitor effects self‐irradiation upon...

We report the synthesis of five new hybrid materials containing [PuCl6]2- anion and charge-balancing, noncovalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals title compounds were grown harvested from acidic, chloride-rich, aqueous media, their structures determined via X-ray diffraction. Compounds 1-4, (4XPyH)2[PuCl6], 5, (4IPyH)4[PuCl6]·2Cl, exhibit two distinct sheet-like structure types. Structurally relevant interactions tabulated crystallographic data...

Lanthanide-containing materials are of interest in the field crystal engineering because their unique properties and distinct structure types. In this context, a new samarium–sodium heterometallic coordination polymer, poly[tetrakis(μ 2 -2-formyl-6-methoxyphenolato)samarium(III)sodium(I)], {[SmNa(C 8 H 7 O 3 ) 4 ]·solvent} n ( Sm-1 ), was synthesized crystallized via slow evaporation from mixture ethanol acetonitrile. The compound features alternating Sm III Na I ions, which linked by ortho...