Functionalization of Tetraphosphido Ligands by Heterocumulenes.

Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P-P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P-C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).

Recycling of Spent FCC Catalysts: Conversion of Leached Residues to Zeolite ZSM-5.

The commercial recycling of spent FCC catalyst typically focuses on recovering only 1-3 % of rare-earth elements, with the remaining residues often disposed of in landfills. Here, we present a novel method to close a recycling loop for spent FCC catalyst. The method involves a series of leaching steps: Firstly, the spent catalyst material is leached with HNO3 to remove rare-earth elements such as La; second, solvothermal leaching with HCl removes most of Al and impurities like Fe, Ni and V; finally, a third leaching with H2SO4 removes Ti. The solid residues are then used to synthesize ZSM-5 without the addition of any extra silicon or aluminum sources after mild activation. The impurities in the synthesis gel strongly modify the properties of the zeolite, with ZSM-5 crystals containing higher levels of impurities exhibiting lower crystallinities, surface areas, acidities, cracking activities, as well as larger particle sizes.

Cobalt-Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides.

Despite the accessibility of numerous transition metal polyphosphido complexes through transition-metal-mediated activation of white phosphorus, the targeted functionalization of Pn ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo-P4 ligands, leading to the discovery of acylcyanophosphanides and -phosphines. Treatment of the complex [K(18c-6)][(Ar*BIAN)Co(η4 -P4 )] ([K(18c-6)]3, 18c-6=[18]crown-6, Ar*=2,6-dibenzhydryl-4-isopropylphenyl, BIAN=1,2-bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η4 -P4 C(O)R)] (R=tBu, Cy, 1-Ad, Ph; 4 a-d). Subsequent reactions of 4 a-d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN]- (9 a-d- ) and the cyclo-P3 cobaltate anion [(Ar*BIAN)Co(η3 -P3 )(CN)]- (8- ). Further reactions of 4 a-d with trimethylsilyl cyanide (Me3 SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P4 C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c-6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O))2 PCN (10).

Visible-Light-Triggered Photoswitching of Diphosphene Complexes.

Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [(2-κ2 P,κ6 C)Mo(CO)2 ][OTf] (3 a[OTf]), [(2-κ2 P,κ6 C)Fe(CO)][OTf] (3 b[OTf]), and [(2-κ2 P)Fe(CO)4 ][OTf] (4[OTf]) were prepared using the triflate salt [(LC )P=P(Dipp)][OTf] (2[OTf) as a precursor (LC =4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate). Upon exposure to blue or UV light (λ=400 nm, 470 nm), the initially red-colored η2 -diphosphene complexes 3 a,b[OTf] readily undergo isomerization to form blue-colored η1 -complexes [(2-κ1 P,κ6 C)M(CO)n ][OTf] (5 a,b[OTf]; a: M=Mo, n=2; b: M=Fe, n=1). This haptotropic rearrangement is reversible, and the (κ2 P,κ6 C)-coordination mode gradually reverts back upon dissolution in coordinating solvents or more rapidly upon exposure to yellow or red irradiation (λ=590 nm, 630 nm). The electronic reasons for the reversible visible-light-induced photoswitching observed for 3 a,b[OTf] are elucidated by DFT calculations. These calculations indicate that the photochromic isomerization originates from the S1 excited state and proceeds through a conical intersection.

Curved graphene nanoribbons derived from tetrahydropyrene-based polyphenylenes via one-pot K-region oxidation and Scholl cyclization.

Precise synthesis of graphene nanoribbons (GNRs) is of great interest to chemists and materials scientists because of their unique opto-electronic properties and potential applications in carbon-based nanoelectronics and spintronics. In addition to the tunable edge structure and width, introducing curvature in GNRs is a powerful structural feature for their chemi-physical property modification. Here, we report an efficient solution synthesis of the first pyrene-based GNR (PyGNR) with curved geometry via one-pot K-region oxidation and Scholl cyclization of its corresponding well-soluble tetrahydropyrene-based polyphenylene precursor. The efficient A2B2-type Suzuki polymerization and subsequent Scholl reaction furnishes up to ∼35 nm long curved GNRs bearing cove- and armchair-edges. The construction of model compound 1, as a cutout of PyGNR, from a tetrahydropyrene-based oligophenylene precursor proves the concept and efficiency of the one-pot K-region oxidation and Scholl cyclization, which is clearly revealed by single crystal X-ray diffraction analysis. The structure and optical properties of PyGNR are investigated by Raman, FT-IR, solid-state NMR, STM and UV-Vis analysis with the support of DFT calculations. PyGNR exhibits a narrow optical bandgap of ∼1.4 eV derived from a Tauc plot, qualifying as a low-bandgap GNR. Moreover, THz spectroscopy on PyGNR estimates its macroscopic charge mobility µ as ∼3.6 cm2 V-1 s-1, outperforming several other curved GNRs reported via conventional Scholl reaction.

A Review of Electrolyte Additives in Vanadium Redox Flow Batteries.

Vanadium redox flow batteries (VRFBs) are promising candidates for large-scale energy storage, and the electrolyte plays a critical role in chemical-electrical energy conversion. However, the operating temperature of VRFBs is limited to 10-40 °C because of the stability of the electrolyte. To overcome this, various chemical species are added, but the progress and mechanism have not been summarized and discussed yet. This review summarizes research progress on electrolyte additives that are used for different purposes or systems in the operation of VRFBs, including stabilizing agents (SAs) and electrochemical mass transfer enhancers (EMTEs). Additives in vanadium electrolytes that exhibit microscopic stabilizing mechanisms and electrochemical enhancing mechanisms, including complexation, electrostatic repulsion, growth inhibition, and modifying electrodes, are also discussed, including inorganic, organic, and complex. In the end, the prospects and challenges associated with the side effects of additives in VRFBs are presented, aiming to provide a theoretical and comprehensive reference for researchers to design a higher-performance electrolyte for VRFBs.

Formation of a Hexaphosphido Cobalt Complex through P-P Condensation.

The reaction between diphosphorus derivatives [(Cl ImDipp )P2 (Dipp)]OTf (1[OTf]) and [(Cl ImDipp )P2 (Dipp)Cl] (1[Cl]) with the cyclotetraphosphido cobalt complex [K(18c-6)][(PHDI)Co(η4 -cyclo-P4 )] (2) leads to the formation of complex [(PHDI)Co{η4 -cyclo-P6 (Dipp)(Cl ImDipp )}] (3), which features an unusual hexaphosphido ligand [Cl ImDipp =4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)imidazol-2-yl, Dipp=2,6-diisopropylphenyl, 18c-6=18-crown-6, PHDI=bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine]. Complex 3 was obtained as a crystalline material with a moderate yield at low temperature. Upon exposure to ambient temperature, compound 3 slowly transforms into two other compounds, [K(18c-6)][(PHDI)Co(η4 -P7 Dipp)] (4) and [(PHDI)Co{cyclo-P5 (Cl ImDipp )}] (5). The novel complexes 3-5 were characterized using multinuclear NMR spectroscopy and single-crystal X-ray diffraction. To shed light on the formation of these compounds, a proposed mechanism based on 31 P NMR monitoring studies is presented.

Structure-Activity Relationships of Triphenylethylene Derivatives and Their Evaluation as Anticancer and Antiviral Agents.

Tamoxifen (TAM) is a selective estrogen receptor modulator (SERM) that is used in the treatment of breast cancer, yet with the risk of developing uterine cancer. A perfect SERM would act as an estrogen activator on bones, the cardiovascular system, and the central nervous system while providing neutral or estrogen blocking effects on the breast and the uterus. Herein, we report on the design, synthesis, and evaluation of new rigid and flexible TAM analogues. Mainly, a chloro substituent is introduced at the para position of the TAM ring C blocking the CYP2D6 hydroxylation site. Most compounds showed estrogenic activity higher than TAM using the yeast estrogen screen assays, indicating the determinant role of the chloro substituent upon functional activity. Despite being estrogenic, compound 2B showed potent antiproliferative activity in the NCI 60 cell lines with mean GI50 = 3.67 µM, GI50 = 1.05 µM on MCF-7 cell lines, and GI50 = 1.30 µM on MDA-MB-231. The estrogenic activity of compound 2B was further confirmed by stimulating alkaline phosphatase in Ishikawa cells, and it showed no increase in relative uterine wet weight in ovariectomized rats. Compound 2F showed EC90 = 0.31 µg/mL and SI90 = 60 against Ebola virus; this is 200-fold more potent than the positive control favipiravir. This is the first time to report estrogenic triphenylethylenes as anti-EBOV agents. The anti-EBOV activity reported is a function of the substitution pattern of the scaffold rather than the functional activity. Moreover, compound 3D showed excellent PO pharmacokinetic properties in mice. In conclusion, for this class of TAM-like compounds, the blockage of the p-position of ring C is decisive for the functional activity; meanwhile, the triarylethylene substitution pattern is detrimental for the antiviral activity.

Cationic Phosphinidene as a Versatile P1 Building Block: [LC-P]+ Transfer from Phosphonio-Phosphanides [LC-P-PR3]+ and Subsequent LC Replacement Reactions (LC = N-Heterocyclic Carbene).

Cationic imidazoliumyl(phosphonio)-phosphanides [LC-P-PR3]+ (1a-e+, LC = 4,5-dimethyl-1,3-diisopropylimidazolium-2-yl; R = alkyl, aryl) are obtained via the nucleophilic fragmentation of tetracationic tetraphosphetane [(LC-P)4][OTf]4 (2[OTf]4) with tertiary phosphanes. They act as [LC-P]+ transfer reagents in phospha-Wittig-type reactions, when converted with various thiocarbonyls, giving unprecedented cationic phosphaalkenes [LC-P═CR2]+ (5a-f[OTf]) or phosphanides [LC-P-CR(NR2')]+ (6a-d[OTf]). Theoretical calculations suggest that three-membered cyclic thiophosphiranes are crucial intermediates of this reaction. To test this hypothesis, treatment of [LC-P-PPh3]+ with phosphaalkenes, that are isolobal to thioketones, permits the isolation of diphosphirane salts 11a,b[OTf]. Furthermore, preliminary studies suggest that the cationic phosphaalkene [LC-P═CPh2]+ may be employed to access rare examples of η2-P═C π-complexes with Pd0 and Pt0 when treated with [Pd(PPh3)4] and [Pt(PPh3)3] for which analogous complexes of neutral phosphaalkenes are scarce. The versatility of [LC-P]+ as a valuable P1 building block was showcased in substitution reactions of the transferred LC-substituent using nucleophiles. This is demonstrated through the reactions of 5a[OTf] and 6c[OTf] with Grignard reagents and KNPh2, providing a convenient, high-yielding access to MesP═CPh2 (16) and otherwise difficult-to-synthesize 1,3-diphosphetane 17 and P-aminophosphaalkenes.

Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation.

Highly selective rare-earth separation has become increasingly important due to the indispensable role of these elements in various cutting-edge technologies including clean energy. However, the similar physicochemical properties of rare-earth elements (REEs) render their separation very challenging, and the development of new selective receptors for these elements is potentially of very considerable economic and environmental importance. Herein, we report the development of a series of 4-phosphoryl pyrazolone receptors for the selective separation of trivalent lanthanum, europium, and ytterbium as the representatives of light, middle, and heavy REEs, respectively. X-ray crystallography studies were employed to obtain solid-state structures across 11 of the resulting complexes, allowing comparative structure-function relationships to be probed, including the effect of lanthanide contraction that occurs along the series from lanthanum to europium to ytterbium and which potentially provides a basis for REE ion separation. In addition, the influence of ligand structure and lipophilicity on lanthanide binding and selectivity was systematically investigated via n-octanol/water distribution and liquid-liquid extraction (LLE) studies. Corresponding stoichiometry relationships between solid and solution states were well established using slope analyses. The results provide new insights into some fundamental lanthanide coordination chemistry from a separation perspective and establish 4-phosphoryl pyrazolone derivatives as potential practical extraction reagents for the selective separation of REEs in the future.

Selective Separation of Lithium, Magnesium and Calcium using 4-Phosphoryl Pyrazolones as pH-Regulated Receptors.

Ensuring continuous and sustainable lithium supply requires the development of highly efficient separation processes such as LLE (liquid-liquid extraction) for both primary sources and certain waste streams. In this work, 4-phosphoryl pyrazolones are used in an efficient pH-controlled stepwise separation of Li+ from Ca2+ , Mg2+ , Na+ and K+ . The factors affecting LLE process, such as the substitution pattern of the extractant, diluent/water distribution, co-ligand, pH, and speciation of the metal complexes involved, were systematically investigated. The maximum extraction efficiency of Li+ at pH 6.0 was 94 % when Mg2+ and Ca2+ were previously separated at pH<5.0, proving that the separation of these ions is possible by simply modulating the pH of the aqueous phase. Our study points a way to separation of lithium from acid brine or from spent lithium ion battery leaching solutions, which supports the future supply of lithium in a more environmentally friendly and sustainable manner.

Crucial Role of Silica-Alumina Binder Mixtures for Hydrocarbon Cracking with ZSM-5 Additives.

Alumina-containing binders are widely used for the binding of catalyst particles by spray drying and calcination. As a part of the active matrix, they contribute to the catalytic performance of the resulting catalyst grain during hydrocarbon cracking. In this study, correlations are investigated using different compositions of Al- and Si-based binders (AlCl3 and colloidal silica) together with kaolin as a filler and ZSM-5 zeolite as an active compound. It was demonstrated that the conversion of a 50:50 hexane mixture, the selectivity toward unsaturated hydrocarbons, and the shape-selective conversion of the hexane feed are highly dependent on the amount and distribution of alumina in binder formulations. While silica species are distributed near the outer shell of catalyst grains, the alumina species are distributed evenly as an adhesive between the catalyst compounds ZSM-5 and kaolin. An optimum amount of alumina in binder formulations results in an increasing conversion of hydrocarbon feedstock due to optimum in active-site accessibility but only a slight decrease in shape-selective properties compared to pure ZSM-5, resulting in an optimum yield of light olefins, especially propylene.

Homoatomic cations: From [P5]+ to [P9].

Recent synthetic approaches to a series of [P9]X salts (X = [F{Al(ORF)3}2], [Al(ORF)4], and (RF = C(CF3)3); Ga2Cl7) overcome limitations in classical synthesis methods that proved unsuitable for phosphorus cations. These salts contain the homopolyatomic cation [P9]+ via (I) oxidation of P4 with NO[F{Al(ORF)3}2], (II) the arene-stabilized Co(I) sandwich complex [Co(arene)2][Al(ORF)4] [arene = ortho-difluorobenzene (o-DFB) and fluorobenzene (FB)], or (III) the reduction of [P5Cl2][Ga2Cl7] with Ga[Ga2Cl7] as Ga(I) source in the presence of P4. Quantum chemical CCSD(T) calculations suggest that [P9]+ formation from [Co(arene)2]+ occurs via the nido-type cluster [(o-DFB)CoP4]+, which resembles the isoelectronic, elusive [P5]+. Apparently, the nido-cation [P5]+ forms intermediately in all reactions, particularly during the Ga(I)-induced reduction of [P5Cl2]+ and the subsequent pick up of P4 to yield the final salt [P9][Ga2Cl7]. The solid-state structure of [P9][Ga2Cl7] reveals the anticipated D2d-symmetric Zintl-type cage for the [P9]+ cation. Our approaches show great potential to bring other [Pn]+ cations from the gas to the condensed phase.

Surface ion-imprinted brewer's spent grain with low template loading for selective uranyl ions adsorption from simulated wastewater.

Efficient removal of uranyl ions from wastewater requires excellent selectivity of the adsorbents. Herein, we report a new strategy using a high monomer/template molar ratio of 500:1 to prepare surface ion-imprinted brewer's spent grain (IIP-BSG) for selective U(VI) removal using binary functional monomers (2-hydroxyethyl methacrylate and diethyl vinylphosphonate) with high site accessibility and easy template removal. IIP-BSG exhibits a maximum U(VI) adsorption capacity of 165.7 mg/g, a high selectivity toward U(VI) in the presence of an excess amount of Eu(III) (Eu/U molar ratio = 20), a good tolerance of salinity, and a high reusability. In addition, mechanism studies have revealed electrostatic interaction and a coordination of uranyl ions by carboxyl and phosphoryl groups, the predominant contribution of high-energy (specific) sites during selective adsorption, and internal mass transfer as the rate-controlling step of U(VI) adsorption. Furthermore, IIP-BSG shows great potentials to separate U(VI) from lanthanides in simulated nuclear wastewater (pH0 = 3.5) and selectively concentrate U(VI) from simulated mine water (pH0 = 7.1). This study proves that the ion-imprinting effect can be achieved using a very low template amount with reduced production cost and secondary pollution, which benefits large-scale promotion of the ion-imprinted materials for selective uranyl ions removal.

Binder Selection to Modify Hydrocarbon Cracking Properties of Zeolite-Containing Composites.

Activity, selectivity, and deactivation behavior of catalyst materials determine their efficiency in hydrocarbon conversion processes. For hydrocarbon cracking, the industrial catalyst is an important parameter in reaction technology to produce valuable compounds, e.g., light olefins (C3-C5) and gasoline from crude oil fractions with high molecular weight (C16+). One strategy to enhance the catalytic activity for precracking is increasing the matrix activity, which depends on the used binder and additives. In this work, three binders (water glass, aluminum chloride, and a mixture of colloidal silica with aluminum dihydrogen phosphate) were used in combination with active zeolite Y, kaolin as filler, and ZSM-5 as additive to produce composite materials. Specific surface area and surface acidity measurements were combined with catalytic testing of the formulated samples in order to find the relation between the catalyst morphology and its activity. In addition, constraint index was used as a control parameter for the determination of the shape-selective properties and their correlation with the catalytic activity. The results show that the binders determine the porosity of the matrix and so the accessibility to zeolite pores and active sites. Matrixes with low porosity and activity enhance coke production and deactivate faster than matrixes with mesopores. Furthermore, ZSM-5 modifies the individual morphological and catalytic effects of the binders. Everything considered, the small crystals of ZSM-5 together with mesopores increase the olefins yield, reduce coking, and therefore enhance the performance of the final grain.

One-pot synthesis of brewer's spent grain-supported superabsorbent polymer for highly efficient uranium adsorption from wastewater.

High-efficient and fast adsorption of uranium is important to reduce the hazards caused by the uranium contamination of water environment due to the increased human activities. Herein, brewer's spent grain (BSG)-supported superabsorbent polymers (SAP) with different cross-linking densities are prepared as cheap and eco-friendly adsorbents for the first time via one-pot swelling and graft polymerization. A 7 wt% NaOH solution is used to swell BSG before grafting and subsequently neutralize the acrylic acid to control the reaction rate without producing alkaline wastewater. Compared with the traditional methods, swelling improves the grafting density and the utilization of raw materials due to the increased disorder degree of the BSG fibers. This results in the grafting of abundant carboxyl and amide groups onto the BSG backbone, forming a strongly hydrophilic polymer network of the BSG-SAP. Compared with the reference polymers without BSG, BSG-SAP presents higher adsorption capacity and enhanced reusability. The highly cross-linked BSG-SAP (BSG-SAP-H) shows an outstanding adsorption capacity of U(VI) (1465 mg/g at pH0 = 4.6), a fast adsorption rate (81% of equilibrium adsorption capacity in 15 min), and a high selectivity in the presence of competing ions. Adsorption mechanism studies reveal the involvement of amide groups, a bidentate binding structure between UO22+ and the carboxyl groups, and a cation exchange between Na+ and UO22+. More importantly, the adsorption capacity of BSG-SAP-H reaches 254.4 mg/g in the fixed-bed column experiment at a low initial concentration (c0(U) = 30 mg/L) and keeps 80% of the adsorption capacity after four cycles, indicating a great potential for uranium removal from wastewater. This work shows a suitable approach to explore the untreated biomass to prepare SAP with enhanced adsorption performance via a general and low-cost strategy.

Direct conversion of white phosphorus to versatile phosphorus transfer reagents via oxidative onioation.

The main feedstock for the value-added phosphorus chemicals used in industry and research is white phosphorus (P4), from which the key intermediate for forming P(III) compounds is PCl3. Owing to its high reactivity, syntheses based on PCl3 are often accompanied by product mixtures and laborious work-up procedures, so an alternative process to form a viable P(III) transfer reagent is desirable. Our concept of oxidative onioation, where white phosphorus is selectively converted into triflate salts of versatile P1 transfer reagents such as [P(LN)3][OTf]3 (LN is a cationic, N-based substituent; that is, 4-dimethylaminopyridinio), provides a convenient alternative for the implementation of P-O, P-N and P-C bonds while circumventing the use of PCl3. We use p-block element compounds of type RnE (for example, Ph3As or PhI) to access weak adducts between nitrogen Lewis bases LN and the corresponding dications [RnELN]2+. The proposed equilibrium between [RnELN]2+ + LN and [RnE(LN)2]2+ allows for the complete oxidative onioation of all six P-P bonds in P4 to yield highly reactive and versatile trications [P(LN)3]3+.

Large Acene Derivatives with B-N Lewis Pair Doping: Synthesis, Characterization, and Application.

Here, we report the synthesis of a novel class of B-N Lewis pair (LPB/N)-doped large acene derivatives (1a-1d) from the well-designed phenanthridine-based precursors. The resultant LPB/N-doped benzo-tetracene (1a), dibenzo-heptacene (1b), dibenzo-octacene (1c), and V-shaped tribenzo-nonacene (1d) are thoroughly characterized by X-ray crystallography, cyclic voltammetry, UV-vis absorption, and fluorescence spectroscopies together with DFT calculations. As a proof of concept, a 1a-based organic light-emitting diode device is fabricated to demonstrate the promising application in organic optoelectronics.

Insights at the molecular level into the formation of oxo-bridged trinuclear uranyl complexes.

Reaction of 1,3,4,6-tetra-O-acetyl-N-(2-hydroxy)-naphthylidene glucosamine (HL(Ac)) with uranyl acetate in ethanol leads to formation of dinuclear [(UO2)2(L)2] (1). In a second step 1 is quantitatively transferred into the trinuclear oxo-bridged complex [(UO2)3(µ3-O)(L)3]2- (22-) via deprotonation and coordination of a water molecule. This transformation was followed by NMR and UV/Vis spectroscopy and it proved possible to selectively introduce 18O into the µ3-bridge.