4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex.

Dilanthanide complexes with one-electron delocalization are important targets for understanding the specific 4f/5d-bonding feature in lanthanide chemistry. Here, we report an isolable azide-bridged dicerium complex 3 [{(TrapenTMS)Ce}2(µ-N3)]• [Trapen = tris (2-aminobenzyl)amine; TMS = SiMe3], which is synthesized by the reaction of tripodal ligand-supported (TrapenTMS)CeIVCl complex 2 with NaN3. The structure and bonding nature of 3 are fully characterized by X-ray crystal diffraction analysis, electron paramagnetic resonance (EPR), magnetic measurement, cyclic voltammetry, X-ray absorption spectroscopy, and quantum-theoretical studies. Complex 3 presents a trans-bent central Ce-N3-Ce unit with a single electron of two mixed-valent Ce atoms. The unique low-temperature (2 K) anisotropic EPR signals [g = 1.135, 2.003, and 3.034] of 3 indicate that its spin density is distributed on the central Ce-N3-Ce unit with marked electron delocalization. Quantum chemical analyses show strong 4f/5d orbital mixing in the singly occupied molecular orbital of 3, which allows for the unpaired electron to extend throughout the cerium-azide-cerium unit via a multicentered one-electron (Ce-N3-Ce) interaction. This work extends the family of mixed-valent dilanthanide complexes and provides a paradigm for understanding the bonding motif of ligand-bridged dilanthanide complexes.

Th6-Based Multicomponent Heterometallic Metal-Organic Frameworks Featuring 6,12-Connected Topology for Iodine Adsorption.

Its high coordination number and tendency to cluster make Th4+ suitable for constructing metal-organic frameworks (MOFs) with novel topologies. In this work, two novel thorium-based heterometallic MOF isomers (IHEP-17 and IHEP-18) were assembled from a Th6 cluster, a multifunctional organic ligand [4-(1H-pyrazol-4-yl)benzoic acid (HPyba)], and Cu2+/Ni2+ cations via the one-pot solvothermal synthesis strategy. The framework features a 6,12-connected new topology net and contains two kinds of supramolecular cage structures, Th36M4 and Th24M2, suitable for guest exchange. Both MOF materials can efficiently adsorb I2. X-ray photoelectron spectroscopy, Raman spectroscopy, and single-crystal X-ray diffraction indicate that the adsorbed iodine is uniformly distributed within the Th36M4 cage but not the Th24M2 cage in the form of I3-.

Colossal negative thermal expansion in a cucurbit[8]uril-enabled uranyl-organic polythreading framework via thermally induced relaxation.

It is an ongoing goal to achieve the effective regulation of the thermal expansion properties of materials. In this work, we propose a method for incorporating host-guest complexation into a framework structure and construct a flexible cucurbit[8]uril uranyl-organic polythreading framework, U3(bcbpy)3(CB8). U3(bcbpy)3(CB8) can undergo huge negative thermal expansion (NTE) and has a large volumetric coefficient of -962.9 × 10-6 K-1 within the temperature range of 260 K to 300 K. Crystallographic snapshots of the polythreading framework at various temperatures reveal that, different from the intrinsic transverse vibrations of the subunits of metal-organic frameworks (MOFs) that experience NTE via a well-known hinging model, the remarkable NTE effect observed here is the result of a newly-proposed thermally induced relaxation process. During this process, an extreme spring-like contraction of the flexible CB8-based pseudorotaxane units, with an onset temperature of ∼260 K, follows a period of cumulative expansion. More interestingly, compared with MOFs that commonly have relatively strong coordination bonds, due to the difference in the structural flexibility and adaptivity of the weakly bonded U3(bcbpy)3(CB8) polythreading framework, U3(bcbpy)3(CB8) shows unique time-dependent structural dynamics related to the relaxation process, the first time this has been reported in NTE materials. This work provides a feasible pathway for exploring new NTE mechanisms by using tailored supramolecular host-guest complexes with high structural flexibility and has promise for the design of new kinds of functional metal-organic materials with controllable thermal responsive behaviour.

Unveiling Structural Diversity of Uranyl Compounds of Aprotic 4,4'-Bipyridine N,N'-Dioxide Bearing O-Donors.

As an aprotic O-donor ligand, 4,4'-bipyridine N,N'-dioxide (DPO) shows good potential for the preparation of uranyl coordination compounds. In this work, by regulating reactant compositions and synthesis conditions, diverse coordination assembly between uranyl and DPO under different reaction conditions was achieved in the presence of other coexisting O-donors. A total of ten uranyl-DPO compounds, U-DPO-1 to U-DPO-10, have been synthesized by evaporation or hydro/solvothermal treatment, and the possible competition and cooperation of DPO with other O-donors for the formation of these uranyl-DPO compounds are discussed. Starting with an aqueous solution of uranyl nitrate, it is found that an anionic nitrate or hydroxyl group is involved in the coordination sphere of uranyl in U-DPO-1 ((UO2)(NO3)2(H2O)2·(DPO)), U-DPO-2 ((UO2)(NO3)2(DPO)), and U-DPO-3 ((UO2)(DPO)(µ2-OH)2), where DPO takes three different kinds of coordination modes, i.e. uncoordinated, monodentate, and biconnected. The utilization of UO2(CF3SO3)2 in acetonitrile, instead of an aqueous solution of uranyl nitrate, precludes the participation of nitrate and hydroxyl, and ensures the engagement of DPO ligands (4-5 DPO ligands for each uranyl) in a uranyl coordination sphere of U-DPO-4 ([(UO2)(CF3SO3)(DPO)2](CF3SO3)), U-DPO-5 ([UO2(H2O)(DPO)2](CF3SO3)2) and U-DPO-6 ([(UO2)(DPO)2.5](CF3SO3)2). Moreover, when combined with anionic carboxylate ligands, terephthalic acid (H2TPA), isophthalic acid (H2IPA), and succinic acid (H2SA), DPO works well with them to produce four mixed-ligand uranyl compounds with similar structures of two-dimensional (2D) networks or three-dimensional (3D) frameworks, U-DPO-7 ((UO2)(TPA)(DPO)), U-DPO-8 ((UO2)2(DPO)(IPA)2·0.5H2O), U-DPO-9 ((UO2)(SA)(DPO)·H2O), and U-DPO-10 ((UO2)2(µ2-OH)(SA)1.5(DPO)). Density functional theory (DFT) calculations conducted to probe the bonding features between uranyl ions and different O-donor ligands show that the bonding ability of DPO is better than that of anionic CF3SO3 -, nitrate, and a neutral H2O molecule and comparable to that of an anionic carboxylate group. Characterization of physicochemical properties of U-DPO-7 and U-DPO-10 with high phase purity including infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and luminescence properties is also provided.

Synthesis of Trapen Ligand-Based U(IV) and Th(IV) 2-Phosphaethynolate Complexes and Comparison of Covalency with Corresponding Ti(IV) Analogues.

The involvement of the 2-phosphaethynolate anion species with ambident nucleophilic properties serves as an essential protocol for synthesizing oxygen-bound or phosphorus-bound complexes. This work mainly describes the synthesis and characterization of U, Th, and Ti phosphaethynolate complexes featuring a preferential O-coordination fashion. Among these complexes, the first examples of a Ti(IV)-OCP complex 3A, Th(IV)-OCP complex 3B, and U(IV)-OCP complex 3C were assembled by a salt metathesis reaction between M(TrapenTMS)(Cl) (M = Ti, Th, U) and NaOCP(dioxane)2.5 and were all crystallographically characterized. The structural similarity of this series of phosphaethynolate complexes allows us to compare the bonding properties of d- and f-block elements in the corresponding compounds. The well-established density functional theory (DFT) computational method was employed to explore the electronic structures and covalency in M-O bonding, and the results showed a consistent pattern. The calculation result showed that 2-phosphaethynolate complexes exhibited the covalency trend of U-O > Th-O > Ti-O due to the involvement of 5f orbitals.

Modular Assembly of Isostructural Mixed-Ligand Uranyl Coordination Polymers Based on a Patterning Strategy.

Controlling the orderly assembly of molecular building blocks for the formation of the desired architectural, chemical, and physical properties of the resulting solid-state materials remains a long-term goal and deserves to be examined. In this work, we propose a patterning strategy for modular assembly and structural regulation of mixed-ligand uranyl coordination polymers (CPs) through the combination of couples of organic ligands with complementary molecular geometry and well-matched coordination modes. By using a 5-(p-tolyldiazenyl)isophthalic acid ligand (H2ptdi) with different rigid linear bicarboxylic acid linkers to construct a well-defined ladder-like pattern, five novel isostructural uranyl coordination polymers, [(UO)2(ptdi)(bdc)0.5](dma) (1), [(UO)2(ptdi)(bpdc)0.5](dma) (2), [(UO)2(ptdi)(tpdc)0.5](dma) (3), [(UO)2(ptdi)(ndc)0.5](dma) (4), and [(UO)2(ptdi) (pdc)0.5](dma) (5) {H2bdc, 1,4-dicarboxybenzene; H2bpdc, 4,4'-biphenyldicarboxylic acid; H2tpdc, terphenyl-4,4″-dicarboxylic acid; H2ndc, 2,6-naphthalenedicarboxylic acid; H2pdc, 1,6-pyrenedicarboxylic acid; [dma]+, [(CH3)2NH2]+}, were successfully synthesized. Structural analysis reveals that 1-5 have similar ladder-like units but different sizes of one-dimensional nanochannels and interlayer spacing due to the different lengths and widths of the linkers. Because of the changes in interlayer spacing of these isostructural cationic frameworks, differences in the performance of Eu3+ ion exchange with [dma]+ are observed. Moreover, those compounds with high phase purity have been further characterized by thermogravimetric analysis, infrared spectroscopy, and luminescence spectroscopy, element analysis, PXRD and UV spectroscopy. Among them, compound 3 with strong fluorescence can selectively detect Fe3+ over several competing metal cations in aqueous solution. This work not only provides a feasible patterning method for effectively regulating the modular synthesis of functional coordination polymers but also enriches the library of uranyl-based coordination polymers with intriguing structures and functionality.

Controllable photomechanical bending of metal-organic rotaxane crystals facilitated by regioselective confined-space photodimerization.

Molecular machines based on mechanically-interlocked molecules (MIMs) such as (pseudo) rotaxanes or catenates are known for their molecular-level dynamics, but promoting macro-mechanical response of these molecular machines or related materials is still challenging. Herein, by employing macrocyclic cucurbit[8]uril (CB[8])-based pseudorotaxane with a pair of styrene-derived photoactive guest molecules as linking structs of uranyl node, we describe a metal-organic rotaxane compound, U-CB[8]-MPyVB, that is capable of delivering controllable macroscopic mechanical responses. Under light irradiation, the ladder-shape structural unit of metal-organic rotaxane chain in U-CB[8]-MPyVB undergoes a regioselective solid-state [2 + 2] photodimerization, and facilitates a photo-triggered single-crystal-to-single-crystal (SCSC) transformation, which even induces macroscopic photomechanical bending of individual rod-like bulk crystals. The fabrication of rotaxane-based crystalline materials with both photoresponsive microscopic and macroscopic dynamic behaviors in solid state can be promising photoactuator devices, and will have implications in emerging fields such as optomechanical microdevices and smart microrobotics.

Coordination-Adaptive Polydentate Pseudorotaxane Ligand for Capturing Multiple Uranyl Species.

The propensity of uranyl for hydrolysis in aqueous environments prevents precise control of uranyl species in the scenarios of on-demand separation and tailored synthesis. Herein, using cucurbit[7]uril (CB[7]) as the macrocyclic molecule and 4,4'-bipyridine-N,N'-dioxide (DPO) as the string molecule, we propose a new kind of multidentate pseudorotaxane ligand, DPO@CB[7] for capturing uranyl species at different pH's. With the aprotic nature of DPO for metal coordination, the coordination ability of the DPO@CB[7] ligand is less affected by pH and can work in a wide range of pH's. Furthermore, by adaptive uranyl coordination, this aprotic pseudorotaxane ligand achieves effective recognition for different uranyl species ranging from monomeric to tetrameric originating from hydrolysis at varying pH's, and four novel uranyl-rotaxane compounds (URC1-4) are successfully obtained. Single-crystal X-ray diffraction analysis reveals that the DPO@CB[7] ligand coordinates with uranyl centers from monomeric to tetrameric in four different modes, as a result of structural flexibility of the DPO@CB[7] pseudorotaxane ligand. A detailed discussion for conformation flexibility of the DPO@CB[7] ligand has been conducted on the position changes of the DPO ligand trapped in the CB[7], which thus reveals good adaptivity of DPO@CB[7] that is noncovalently bonded as a supramolecular motif. In addition, characterization of the physicochemical properties of URC1 and URC2 with high phase purity, including powder X-ray diffraction (PXRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), and luminescence properties, are also provided. This work provides a good case of an adaptive pseudorotaxane ligand for the recognition and capture of different uranyl species and will bring valuable hints to the design of multifunctional supramolecular ligands for actinide separation in the future.

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity.

The electron-rich squarate ion (C4O42-, SA2-) possesses electronic delocalization over the entire molecule and good redox activity, and the functionalization of metal-organic complexes with the SA2- group is desirable. In this work, a mixed-ligand method is used to construct novel uranyl squarate coordination polymers utilizing 4,4'-bipyridine (bpy), 4,4'-bipyridine-N,N'-dioxide (bpydo), 1,10-phenanthroline (phen), 4,4'-vinylenedipyridine (vidpy), and in situ formed oxalate (OA2-) as ancillary ligands. Seven mixed-ligand uranyl compounds, [(UO2)(OH)(SA)](Hbpy) (1), [(UO2)(H2O)(SA)2](H2bpy) (2), (UO2)(H2O)(SA)(bpydo)·2H2O (3), (UO2)(H2O)(SA)(phen)·H2O (4), (UO2)(OH)(SA)0.5(phen)·H2O (5), [(UO2)(SA)(OA)0.5](Hphen) (6), and [(UO2)(SA)(OA)0.5](Hvidpy) (7), with varying crystal structures were synthesized under hydrothermal conditions. Compound 1, together with bpy molecules filling in the interlayer space as template agents, has a two-dimensional (2D) network structure, while 2 gives a one-dimensional (1D) chain based on mononuclear uranium units. Compound 3 shows a neutral 2D network through the combined linkage of SA2- and bpydo. Both 4 and 5 have a similar chain-like structure due to the capping effect of phen motifs, while phen molecules in 6 act as templating agents after protonation. Similar to 6, compound 7 has a "sandwich-like" structure in which the Hvidpy motifs locate in the voids of layers of 2D uranyl-squarate networks. The redox properties of typical mixed-ligand uranyl-squarate compounds, 1, 4, and 5 with high phase purity, are characterized using cyclic voltammetry. All three of these uranyl coordination compounds show anode peaks (Ea) at 0.777, 0.804, and 0.760 V, respectively, which correspond to the oxidation process of SA2- → SA. Meanwhile, cathodic peaks (Ec) at -0.328, -0.315, and -0.323 V corresponding to the reduction process of U(VI) → U(V) are also observed. The results reveal that all three of these uranyl coordination compounds show good redox activity and, most importantly, the interplay between two different redox-active motifs of SA2- organic linker and uranyl node. This work enriches the library of redox-active uranyl compounds and provides a feasible mixed-ligand method for regulating the synthesis of functional actinide compounds.

Selective Separation of Am(III)/Eu(III) by the QL-DAPhen Ligand under High Acidity: Extraction, Spectroscopy, and Theoretical Calculations.

Although 1,10-phenanthroline-based ligands have recently shown vast opportunities for the separation of trivalent actinides (Ans(III)) from lanthanides (Lns(III)), the optimization and design of the extractant structure based on the phenanthroline framework remain hotspots for further improving the separation. Following the strategy of hard and soft donor atom combination, for the first time, the quinoline group was attached to the 1,10-phenanthroline skeleton, giving a lipophilic ligand, 2,9-diacyl-bis((3,4-dihydroquinoline-1((2H)-yl)-1),10-phenanthroline (QL-DAPhen)), for Am(III)/Eu(III) separation. In the presence of sodium nitrate, the ligand can effectively extract Am(III) over Eu(III) in HNO3 solution, with the separation factor (SFAm/Eu) ranging from 29 to 44. The coordination chemistry of Eu(III) with QL-DAPhen was investigated by slope analysis, NMR titration, UV-vis titration, Fourier transform infrared spectroscopy, electrospray ionization-mass spectrometry, and theoretical calculations. The experimental results unanimously confirm that the ligand forms both 1:1 and 1:2 complexes with Eu(III), and the stability constants (log ß) of each of the two complexes were obtained. Density functional theory calculations show that the Am-N bonds have more covalent characteristics than the Eu-N bonds in the complexes, which reveals the reason why the ligand preferentially bonds with Am(III). Meanwhile, the thermodynamic analysis reveals that the 1:1 complex is more thermodynamically stable than the 1:2 complex. The findings of this work have laid a solid theoretical foundation for the application of phenanthroline-based ligands in the separation of An(III) from practical systems.

Proximity Effect in Uranyl Coordination of the Cucurbit[6]uril-Bipyridinium Pseudorotaxane Ligand for Promoting Host-Guest Synergistic Chelating.

In the present work, we proposed regulating uranyl coordination behavior of cucurbituril-bipyridinium pseudorotaxane ligand by utilizing meta-functionalized bipyridinium dicarboxylate guest. A tailored pseudorotaxane precursor involving 1,1'-(hexane-1,6-diyl)bis(3-cyanopyridin-1-ium) bromide (C6BPCN3) and cucurbit[6]uril (CB[6]) has designed and synthesized. Through in situ hydrolysis of the pseudorotaxane ligands and their coordination assembly with uranyl cations, seven new uranyl-rotaxane coordination polymers URCP1-URCP7 have been obtained under hydrothermal conditions in the presence of different anions. It is demonstrated that the variation of carboxylate groups from para- to meta-position greatly affected the coordination behaviors of the meta-functionalized pseudorotaxane linkers, which are enriched from simple guest-only binding to host-guest simultaneous coordination and synergistic chelating. This effective regulation on uranyl coordination of supramolecular pseudorotaxane can be attributed to the proximity effect, which refers to the meta-position carboxyl group being spatially closer to the portal carbonyl group of CB[6]. Moreover, by combining other regulation methods such as introducing competing counterions and modulating solution acidity, the nuclearity of the uranyl center and the coordination patterns of the pseudorotaxane ligand can be diversely tuned, which subsequently exert great influence on the final dimensionality of resultant uranyl compounds. This work presents a large diversity of uranyl-based coordination polyrotaxane compounds with fascinating mechanically interlocked components and, most importantly, provides a feasible approach to adjust and control the metal coordination behavior of the pseudorotaxane ligand that might expand the scope of application of such supramolecular ligands.

An Azobenzene-Modified Photoresponsive Thorium-Organic Framework: Monitoring and Quantitative Analysis of Reversible trans-cis Photoisomerization.

Monitoring and quantification of the photoresponsive behavior of metal-organic frameworks that respond to a light stimulus are crucial to establish a clear structure-activity relationship related to light regulation. Herein, we report the first azobenzene-modified photoresponsive thorium-organic framework (Th-Azo-MOF) with the formula [Th6O4(OH)4(H2O)6L6] (H2L = (E)-2'-p-tolyldiazenyl-1,1':4',4'-terphenyl-4,4″-dicarboxylic acid), in which the utilization of a thorium cluster as a metal node leads to one of the largest pore sizes among all the azobenzene-containing metal-organic frameworks (MOFs). The phototriggered transformation of the trans isomer to the cis isomer is monitored and characterized quantitatively by comprehensive analyses of NMR and UV spectroscopy, which reveals that the maximum isomerization ratio of cisTh-Azo-MOF in the solid state is 19.7% after irradiation for 120 min, and this isomerization is reversible and can be repeated several times without apparent performance changes. Moreover, the isomerization-related difference in the adsorption of the Rhodamine B guest is also illustrated and a possible photoregulated mechanism is proposed. This work will shed light on new explorations for constructing functionalized actinide porous materials by the elegant combination of actinide nodes with tailored organic ligands and furthermore will provide a comprehensive understanding of photoisomerization processes in MOF solids and insight into the mechanism on photoregulated cargo adsorption and release by photoactive MOFs.

Solar-Driven Nitrogen Fixation Catalyzed by Stable Radical-Containing MOFs: Improved Efficiency Induced by a Structural Transformation.

Herein we present a new viologen-based radical-containing metal-organic framework (RMOF) Gd-IHEP-7, which upon heating in air undergoes a single-crystal-to-single-crystal transformation to generate Gd-IHEP-8. Both RMOFs exhibit excellent air and water stability as a result of favorable radical-radical interactions, and their long-lifetime radicals result in wide spectral absorption in the range 200-2500 nm. Gd-IHEP-7 and Gd-IHEP-8 show excellent activity toward solar-driven nitrogen fixation, with ammonia production rates of 128 and 220 µmol h-1 g-1 , respectively. Experiments and theoretical calculations indicate that both RMOFs have similar nitrogen fixation pathways. The enhanced catalytic efficiency of Gd-IHEP-8 versus Gd-IHEP-7 is attributed to intermediates stabilized by enhanced hydrogen bonding.

Molecular Spring-like Triple-Helix Coordination Polymers as Dual-Stress and Thermally Responsive Crystalline Metal-Organic Materials.

Elastic metal-organic materials (MOMs) capable of multiple stimuli-responsiveness based on dual-stress and thermally responsive triple-helix coordination polymers are presented. The strong metal-coordination linkage and the flexibility of organic linkers in these MOMs, rather than the 4 Šstacking interactions observed in organic crystals, causes the helical chain to act like a molecular spring and thus accounts for their macroscopic elasticity. The thermosalient effect of elastic MOMs is reported for the first time. Crystal structure analyses at different temperatures reveal that this thermoresponsiveness is achieved by adaptive regulation of the triple-helix chains by fine-tuning the opening angle of flexible V-shaped organic linkers and rotation of its lateral conjugated groups to resist possible expansion, thus demonstrating the vital role of adaptive reorganization of triple-helix metal-organic chains as a molecular spring-like motif in crystal jumping.

A mixed-ligand strategy regulates thorium-based MOFs.

Two novel thorium-based organic frameworks (Th-IHEP-5 and Th-IHEP-6) were assembled from a hexanuclear thorium cluster, porphyrin derivative ligand and linear carboxylic acid ligands via a mixed-ligand strategy. As a stable heterogeneous catalyst, Th-IHEP-5 exhibited high photocatalytic activity for the oxidation of 2-chloroethyl ethyl sulfide (CEES) and the fixation of CO2. The good catalytic effect is attributed to the large conjugated system of porphyrin and the photosensitizer enhancing effects of bipyridine.

Metal-Carboxyl Helical Chain Secondary Units Supported Ion-Exchangeable Anionic Uranyl-Organic Framework.

As a less explored avenue, actinide-based metal-organic frameworks (MOFs) are worth studying for the particularity of actinide nodes in coordination behaviour and assembly modes. In this work, an azobenzenetetracarboxylate-based anionic MOF supported by uranyl-carboxyl helical chain units was synthesized, incorporating linear uranyl as the metal centre. This kind of helical chain-type building unit is reported for the first time in uranyl-based MOFs. Structural analysis reveals that the formation of helical chain secondary units can be attributed to restricted equatorial coordination of rigid flat azobenzene ligand to uranyl centres. Meanwhile, this newly-synthesized anionic material has been used to remove Eu3+ ions, as a non-radioactive surrogate of Am3+ ion, through an ion-exchange process with [(CH3 )2 NH2 ]+ ions in its open channels, as evidenced by a combination of 1 H NMR spectroscopy, EDS and PXRD.

Releasing Metal-Coordination Capacity of Cucurbit[6]uril Macrocycle in Pseudorotaxane Ligands for the Construction of Interwoven Uranyl-Rotaxane Coordination Polymers.

As an emerging type of actinide hybrid material, uranyl-rotaxane coordination polymers (URCPs) with new coordination patterns and topological structures are still desired. In this work, we propose a new strategy to construct URCPs by promoting the simultaneous coordination of both the wheel and axle moieties in pseudorotaxane linkers with metal nodes. Starting from a series of cucurbit[6]uril (CB[6])-based pseudorotaxane ligands, C nBPCA@CB[6] [C nBPCA = 1,1-(α,ω-diyl)bis[4-(ethoxycarbonyl)pyridin-1-ium] bromides, where n = 5-8] with slightly deformed CB[6], four new URCPs (URCP1, URCP3, URCP4, and URCP5) with interwoven network structures, as well as another noninterwoven polymer(URCP2), have been successfully prepared. According to single-crystal structure analysis, we attribute the interwoven structures of the URCPs to the distortion of CB[6] in pseudorotaxane ligands with shorter or longer spacers (C5, C7, and C8). This indicates that the deformation could effectively diminish the steric hindrance around the portals, thus endowing the "inert" CB[6] host with coordination ability like the string molecule. Besides, the participation of water molecules and sulfate anions in the uranyl coordination sphere is also found to have a great influence on the final structures of the obtained URCPs. The successful preparation of interwoven URCPs in this work gives some new insights into the metal coordination of supramolecular entities and could facilitate other new applications of CB[6]-based pseudorotaxane ligands. Most importantly, the strategy proposed in this work provides some hints in the controllable design of metal-organic rotaxane frameworks with unique topologies.

Actinide-Based Porphyrinic MOF as a Dehydrogenation Catalyst.

Uranyl-organic frameworks (UOFs) have recently been the object of many research endeavors due to the unique coordination mode of uranyl ions and their attractive physicochemical properties. Here, a new (3,4)-connected UOF (U-IHEP-4) assembled from uranyl and porphyrin ligand tetrakis(4-carboxyphenyl)porphyrin (H4TCPP) is reported, which represents the first case of actinide porphyrinic MOFs. Adsorption experiments in DMF solution demonstrated that U-IHEP-4 selectively adsorbs positively charged dyes, which is in line with its negatively charged framework and large pore volume ratio (90 %). Remarkably, U-IHEP-4 exhibited high catalytic activity for the dehydrogenation of N-heterocycles to synthesize the corresponding aromatic heterocycles and it can be used as an efficient heterogeneous catalyst.

Large-Pore 3D Cubic Mesoporous (KIT-6) Hybrid Bearing a Hard-Soft Donor Combined Ligand for Enhancing U(VI) Capture: An Experimental and Theoretical Investigation.

A preorganized tetradentate phenanthrolineamide (DAPhen) ligand with hard and soft donors combined in the same molecule has been found to possess high extraction ability toward actinides over lanthanides from acidic aqueous solution in our previous work. Herein we grafted phenanthrolineamide groups onto a large-pore three-dimensional cubic silica support by the reaction of DAPhen siloxane with KIT-6 substrate to prepare a novel uranium-selective sorbent, KIT-6-DAPhen. The as-synthesized sorbent was well-characterized by scanning electron microscopy, high-resolution transmission electron microscopy, N2 adsorption/desorption, X-ray diffraction, FT-IR, 13C cross-polarization magic-angle spinning NMR, and TGA techniques, which confirmed the consummation of the functionalization. Subsequently, the effects of contact time, solution pH, initial U(VI) concentration, and the presence of competing metal ions on the U(VI) sorption onto KIT-6-DAPhen sorbent were investigated in detail. It was found that KIT-6-DAPhen showed largely enhanced sorption capacity and excellent selectivity toward U(VI). The maximum sorption capacity of KIT-6-DAPhen at pH 5.0 reaches 328 mg of U/g of sorbent, which is superior to most of functionalized mesoporous silica materials. Density functional theory coupled with quasi-relativistic small-core pseudopotentials was used to explore the sorption interaction between U(VI) and KIT-6-DAPhen, which gives a sorption reaction of KIT-6-DAPhen + [UO2(H2O)5]2+ + NO3- ⇄ [UO2(KIT-6-DAPhen)(NO3)]+ + 5H2O. The findings of the present work provide new clues for developing new actinide sorbents by combining new ligands with various mesoporous matrixes.