RESUMEN
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.
RESUMEN
The attributes of good solubility and the redox-neutral nature of molten salt fluxes enable them to be useful for the synthesis of novel crystalline actinide compounds. In this work, a flux growth method under an inert atmosphere is proposed to explore the valence diversity of uranium, and a series of five uranium silicate structures, [K3Cl][(UVIO2)(Si4O10)] (1), Cs3[(UVO2)(Si4O10)] (2), K2[UIV(Si2O7)] (3), K8[(UVIO2)(UVO2)2(Si8O22)] (4), and Cs6[UIV(UVO)2(Si12O32)] (5), were synthesized using different metal halide salt and feeding U/Si ratios. Crystal structure analysis reveals that the utilization of argon atmosphere that helps to avoid possible oxidation of low-valence uranium generates a variety of oxidation states of uranium including U(VI), U(V), U(IV), mixed-valence U(V) and U(VI), and mixed-valence U(IV) and U(V). Characterization of physicochemical properties of representative compounds shows that all these uranium silicate compounds have bandgaps among the range of 2.0-3.4 eV, and mixed-valence uranium silicate compounds have relatively narrower bandgaps. Density functional theory calculations on formation enthalpies, lattice energies, and bandgaps of all five compounds were also performed to provide more structural information about these uranium silicates. This work enriches the library of variable-valence uranium silicate compounds and provides a feasible way to produce novel actinide compounds with intriguing properties through the flux growth method that might show potential application in relevant fields such as storage media for nuclear waste.
RESUMEN
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-.
RESUMEN
Efficient transfer of charge carriers through a fast transport pathway is crucial to excellent photocatalytic reduction performance in solar-driven CO2 reduction, but it is still challenging to effectively modulate the electronic transport pathway between photoactive motifs by feasible chemical means. In this work, we propose a thermally induced strategy to precisely modulate the fast electron transport pathway formed between the photoactive motifs of a porphyrin metal-organic framework using thorium ion with large ionic radius and high coordination number as the coordination-labile metal node. As a result, the stacking pattern of porphyrin molecules in the framework before and after the crystal transformations has changed dramatically, which leads to significant differences in the separation efficiency of photogenerated carriers in MOFs. The rate of photocatalytic reduction of CO2 to CO by IHEP-22(Co) reaches 350.9 µmol·h-1·g-1, which is 3.60 times that of IHEP-21(Co) and 1.46 times that of IHEP-23(Co). Photoelectrochemical characterizations and theoretical calculations suggest that the electron transport channels formed between porphyrin molecules inhibit the recombination of photogenerated carriers, resulting in high performance for photocatalytic CO2 reduction. The interaction mechanism of CO2 with IHEP-22(Co) was clarified by using in-situ electron paramagnetic resonance, in-situ diffuse reflectance infrared Fourier transform spectroscopy, in-situ extended X-ray absorption fine structure spectroscopy, and theoretical calculations. These results provide a new method to regulate the efficient separation and migration of charge carriers in CO2 reduction photocatalysts and will be helpful to guide the design and synthesis of photocatalysts with superior performance for the production of solar fuels.
RESUMEN
Moisture harvesters with favourable attributes such as easy synthetic availability and good processability as alternatives for atmospheric moisture harvesting (AWH) are desirable. This study reports a novel nonporous anionic coordination polymer (CP) of uranyl squarate with methyl viologen (MV2+ ) as charge balancing ions (named U-Squ-CP) which displays intriguing sequential water sorption/desorption behavior as the relative humidity (RH) changes gradually. The evaluation of AWH performance of U-Squ-CP shows that it can absorb water vapor under air atmosphere at a low RH of 20 % typical of the levels found in most dry regions of the world, and have good cycling durability, thus demonstrating the capability as a potential moisture harvester for AWH. To the authors' knowledge, this is the first report on non-porous organic ligand bridged CP materials for AWH. Moreover, a stepwise water-filling mechanism for the water sorption/desorption process is deciphered by comprehensive characterizations combining single-crystal diffraction, which provides a reasonable explanation for the special moisture harvesting behaviour of this non-porous crystalline material.
RESUMEN
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 â¼260 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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
Separation of Cs/Sr is one of many coordination-chemistry-centered processes in the grand scheme of spent nuclear fuel reprocessing, a critical link for a sustainable nuclear energy industry. To deploy a crystallizing Cs/Sr separation technology, we planned to systematically screen and identify candidate ligands that can efficiently and selectively bind to Sr2+ and form coordination polymers. Therefore, we mined the Cambridge Structural Database for characteristic structural information and developed a machine-learning-guided methodology for ligand evaluation. The optimized machine-learning model, correlating the molecular structures of the ligands with the predicted coordinative properties, generated a ranking list of potential compounds for Cs/Sr selective crystallization. The Sr2+ sequestration capability and selectivity over Cs+ of the promising ligands identified (squaric acid and chloranilic acid) were subsequently confirmed experimentally, with commendable performances, corroborating the artificial-intelligence-guided strategy.
RESUMEN
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-4,4â³-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.
RESUMEN
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.
RESUMEN
Solar-initiated CO2 reduction is significant for green energy development. Herein, we have prepared a new mesoporous/microporous porphyrin metal-organic framework (MOF), IHEP-20, loaded with polymetallic oxygen clusters (POMs) to form a composite material POMs@IHEP-20 for visible-light-driven photocatalytic CO2 reduction. The as-made composite material exhibits good stability in water from pH 0 to 11. After POMs were introduced to IHEP-20, they showed superior activity toward photocatalytic CO2 reduction with a CO production rate of 970 µmol·g-1·h-1, which is 3.27 times higher than that of pristine IHEP-20. This study opens a new door for the design and synthesis of high-performance catalysts for the photocatalytic reduction of CO2.
RESUMEN
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.
RESUMEN
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- â SA. Meanwhile, cathodic peaks (Ec) at -0.328, -0.315, and -0.323 V corresponding to the reduction process of U(VI) â 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.
RESUMEN
A novel two-dimensional double-layer anionic uranyl-organic framework, U-TBPCA {[NH2(CH3)2][(UO2)(TBPCA)], where H3TBPCA = 4,4',4â³-s-triazine-1,3,5-triyltripamino-methylene-cyclohexane-carboxylate}, with abundant active sites and stability was obtained by assembling UO2(NO3)2·6H2O and a triazine tricarboxylate linker, TBPCA3-. Due to the flexibility of the ligand and diverse coordination modes between carboxyl groups and uranyl ions, U-TBPCA exhibits an intriguing topological structure and steric configuration. This double-layer anionic uranyl-organic framework is highly porous and can be used for selective adsorption of cationic dyes. Due to the presence of high-density metal ions and basic -NH- groups, U-TBPCA acts as an effective heterogeneous catalyst for the cycloaddition reaction of carbon dioxide with epoxy compounds. Moreover, the various modes of coordination between the tricarboxylic ligand and uranyl ion were studied by density functional theory calculations, and several simplified models were established to probe the influence of hydrogen bonding between carbon dioxide and U-TBPCA on the ability of U-TBPCA to bind carbon dioxide. This work should aid in improving our understanding of the coordination behavior of uranyl ion as well as the development and utilization of new actinide materials.
RESUMEN
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.
RESUMEN
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-4,4â³-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.
RESUMEN
Two phenoxo- and cyanido-bridged one-dimensional complexes NiII2GdIII2FeIII3 (1) and NiII2DyIII2FeIII3 (2) have been prepared. They are the first pentacyanidoferrite-bridged heterotrimetallic complexes. Magnetic studies reveal that overall ferromagnetic interactions are present in complexes 1 and 2, and complex 2 shows single-molecule magnet (SMM) behaviour with an energy barrier of 14.8 K.
RESUMEN
Herein, we report a new uranyl-organic polyhedron U4L4 (L = BTPCA) assembled from uranyl and a semirigid tritopic ligand. By adjusting the carbon chain length of organic templates, two complexes can be obtained based on the diverse secondary assembly of U4L4 cages. The mechanism of different arrangements of U4L4 cages induced by organic templates was explored in detail.
RESUMEN
We present here the synthesis of a novel fluorescent actinide polyrotaxane compound URCP1 through the utilization of an end-cutting pseudorotaxane precursor with only the cucurbit[6]uril (CB[6]) macrocyclic components acting as linking struts. The non-coordinating guest motif in the obtained polyrotaxane, with increased freedom and structural flexibility, can display intriguing temperature-triggered conformational variations inside the cavity of CB[6], which was clearly evidenced by crystallographic snapshots at different temperatures. Notably, this observation of temperature-triggered structural dynamics in URCP1 represents the first report of actinide polyrotaxane with such feature in solid-state. Moreover, URCP1 has a high photoluminescence quantum yield (PLQY) of 49.8 %, comparable to other luminescent uranyl compounds, and can work as a fluorescent probe to selectively detect Fe3+ over other eight competing cations in aqueous solution, with the limit of detection being as low as 4.4×10-3 â ppm.