1-hydroxyethylidenediphosphonic Acid Research Articles

Synthesis and In Situ Monitoring of Mechanochemical Preparation of Highly Proton Conductive Hydrogen-Bonded Metal Phosphonates.

Crystalline porous materials are recognized as promising proton conductors for the proton exchange membrane (PEM) in fuel cell technology owing to their tunable framework structure. However, it is still a challenging bulk synthesis for real-world applications of these materials. Herein, we report the mechanochemical gram-scale synthesis of two isostructural metal hydrogen-bonded organic frameworks (MHOFs) of Co(II) and Ni(II) based on 1-hydroxyethylidenediphosphonic acid (HEDPH4) with 2,2'-bipyridine (2,2'-bipy): Co(HEDPH3)2(2,2'-bipy)·H2O (1) and Ni(HEDPH3)2(2,2'-bipy)·H2O (2). In situ monitoring of the mechanochemical synthesis using different synchrotron-based techniques revealed a one-step mechanism - the starting materials are directly converted to the product. With the existence of extensive hydrogen bonds with amphiprotic uncoordinated phosphonate hydroxyl and oxygen atoms, both frameworks exhibited proton conduction in the range of 10-4 S cm-1 at room temperature under humid conditions. This study demonstrates the potential of green mechanosynthesis for bulk material preparation of framework-based solid-state proton conductors.

MIXED-LIGAND GERMANIUM–LANTHANIDE COMPLEXES WITH 1-HYDROXYETHYLIDENEDIPHOSPHONIC ACID AND 2,2’-BIPYRIDINE

There were developed the novel methods for the synthesis of six mixed- metal and mixed-ligand complexes of germanium and rare earth metals (Pr, Nd, Dy, Ho, Tm, Lu) with 1-hydroxyethylidenediphosphonic acid and 2,2´-bipyridine. The compounds have been characterized using various research methods: elemental analysis, mass spectrometry, electrical conductivity, thermogravimetry, IR spectroscopy. It has proved that all complexes are crystal hydrates, belong to heterometallic mixed ligand compounds [Ln(H2O)4(bipy)2]2 [Ge(m-hedp) (m- OH)]6⸱nH2O, Ln=Pr (1); Nd (2); Dy (3); Ho (4); Tm (5); Lu (6); n = 22 (1, 2), 21 (3), 20 (4, 5), 19 (6). Their formation occurs due to the electrostatic interaction of complex cations [Ln(H2O)4(bipy)2]3+ with hexanuclear anions [Ge(m-hedp)(m- OH)]66-. According to the results of measuring the electrical conductivity of dimethylformamide solutions 1–6, it has been established that they belong to triionic electrolytes: λ (in Ohm-1∙сm2∙mol-1) for 1 = 131,3; 2 = 138,8; 3 = 145,8; 4 = 151,1; 5 = 158,3; 6 = 162,7. The cation-anionic type of complexes 1–6 has been confirmed as a result of the analysis of their mass spectrum. The analysis of the mass spectrum showed that the main decomposition direction of the complex is related to the formation of the complex cation fragment [Ln(H2O)4(bipy)2]3+, which corresponds to the most intense peak (m/z = 136, I = 55%). The thermal decomposition of compounds 1–6 includes dehydration, deaquatation, oxidative thermal destruction and the formation of final products as a mixture of Ln2O3 and GeP2O7. On the DTA curves in the interval 70–200 °C the first endothermic effect can be traced, which is accompanied by the removal of a certain number of crystallization and coordination water molecules into the gas phase. Absorption bands of the P-O bond have been detected at ~1053 and ~970 сm-1, that indicates the presence of the fully deprotonated PO32- groups in the composition of complexes. Furthermore, n(OH), ν(Ge–O), d(Ge–OH) bands characteristic for all the previously synthesized compounds with [Ge6(m-OH)6(m-hedp)6]6- anion have been detected in the IR spectra of 1–6. A set of the bands usual for the aromatic molecules n(C–C), das(CH3), ds(CH3), n(Сar=N) has been assigned with 2,2`-bipyridine in the structure of all compounds.

Urea Salts with 1-Hydroxyethylidene Diphosphonic Acid

The reaction of urea with 1-hydroxyethylidene diphosphonic acid in the ratios of 1 : 1, 1 : 2, 1 : 3 was first studied. As a result of the reactions, the corresponding 1 : 2 or 2 : 1 salts were formed, which can exhibit biological activity. The synthesized compounds were characterized by atomic emission spectroscopy, IR and NMR spectroscopy. According to atomic emission analysis, an increase in the amount of urea from 3 moles or more per 1 mole of 1-hydroxyethylidene diphosphonic acid does not cause an increase in the urea content in the final products. According to NMR spectroscopy data, compounds in the formation of which phosphoryl groups of 1-hydroxyethylidene diphosphonic acid are involved are in dynamic equilibrium salt–free acid.

Different Fe(III) and Fe(II) complexes in clonal micropropagation of Gooseberry

Iron chlorosis and tissue necrotization are often problems of plant growth in sterile conditions. Therefore, the overall multiplication factor and the productiveness dramatically decrease. The aim of work paper was to study the effect of various forms of iron chelates, including the stable complex of iron (II) with phosphorus-containing organic ligand, 1-hydroxyethylidenediphosphonic acid (HEDP), to the nutrient medium on the development of micro-shoots of Pink-2 (Rosovy-2) gooseberry cultivar according to Quoirin & Lepoivre (QL). Seven types of media were used in the screening: FeS04×7H20 + Na2EDTA (two control variant); Fe-EDTA - a complex of iron with ethylenediaminotetraacetic acid as such; Fe-DTPA (ferric diethylenetriaminepentaacetate), Fe3+ and Fe2+ -HEDP (ferric (III,II) 1-hydroxy ethylidene-1,1-diphosphonate), Fe-EDDHA (ethylenediamine di-2-hydroxyphenyl acetate ferric). The influence of 4 concentration values of concentrations of introduced iron complexes were studied experimentally: reduced (×0.5), standard (×l), increased 1.5-fold (×l.5) and double concentration (×2). Results have shown that form of introduction of iron sources, the valence of the iron ion, the ligand types and their concentrations are important factors in shoot multiplication of gooseberry cultivar ‘Pink-2’.

An Efficient Cobalt Phosphide Electrocatalyst Derived from Cobalt Phosphonate Complex for All-pH Hydrogen Evolution Reaction and Overall Water Splitting in Alkaline Solution.

The development of low-cost and highly efficient electrocatalysts via an eco-friendly synthetic method is of great significance for future renewable energy storage and conversion systems. Herein, cobalt phosphides confined in porous P-doped carbon materials (Co-P@PC) are fabricated by calcinating the cobalt-phosphonate complex formed between 1-hydroxyethylidenediphosphonic acid and Co(NO3 )2 in alkaline solution. The P-containing ligand in the complex acts as the carbon source as well as in situ phosphorizing agent for the formation of cobalt phosphides and doping P element into carbon material upon calcination. The Co-P@PC exhibits high activity for all-pH hydrogen evolution reaction (overpotentials of 72, 85, and 76 mV in acidic, neutral, and alkaline solutions at the current density of 10 mA cm-2 ) and oxygen evolution reaction in alkaline solution (an overpotential of 280 mV at the current density of 10 mA cm-2 ). The alkaline electrolyzer assembled from the Co-P@PC electrodes delivers the current density of 10 mA cm-2 at the voltage of 1.60 V with a durability of 60 h. The excellent activity and long-term stability of the Co-P@PC derives from the synergistic effect between the active cobalt phosphides and the porous P-doped carbon matrix.

Biodistribution ex vivo of 213Bi-KHEDP − a promising boneseeking agent for targeted alpha therapy

Alpha-emitters are increasingly used for targeted alpha therapy because of their emission of high linear energy transfer (LET) particles with a relative short path length. Bismuth-213 (213Bi, T1/2 = 46 min) is one of the most suitable radiation sources for medical applications. In the present work the biodistribution of 213Bi-monopotassium salt of 1-hydroxyethylidene diphosphonic acid (213Bi-KHEDP) in intact mice was studied. It was shown that bones uptake of 213Bi-KHEDP were higher than in the most soft tissue organs throughout the study. The bone-to-soft tissue ratios for 213Bi-KHEDP were higher than the corresponding data for 213BiCl5. Among the soft tissue organs, only kidneys had a high uptake of Bi-KHEDP and free 213Bi. In conclusion, 213Bi-KHEDP had a strong and selective bone affinity, indicating that this complex could be useful to deliver alpha-particle radiation to primary bone cancer and skeletal metastases.

Synthesis and Structure of Different-Metal Different-Ligand Germanium(IV) and Cobalt(II) or Copper(II) Complexes with 1-Hydroxyethylidenediphosphonic Acid and 1,10-Phenanthroline

Different-metal different-ligand complexes [{Co(Phen)3}2{Co(Phen)(H2O)4}2][{Ge(μ-OH)(μ- Hedp)}6Cl2] (I), [{Cu(Phen)2(H2O)}2(HPhen)2][Ge(μ-OH)(μ-Hedp)]6 · 20H2O (II) (H4Hedp = 1-hydroxyethylidenediphosphonic acid, Phen = 1,10-phenanthroline) were synthesized and studied by X-ray diffraction. According to X-ray diffraction data (CIF files CCDC nos. 1573112 (I), 1573113 (II)), compounds I and II are cation–anion type complexes in which the anions are represented by {[Ge(μ-OH)(μ-Hedp)]6}6– and, in the case of I, two additional Cl– ions, while the cations are [Co(Phen)3]2+, [Co(Phen)(H2O)4]2+ in I and [Cu(Phen)2(H2O)]2+, HPhen+ in II. In the crystals of compounds I and II, the cations, anions, and water molecules are combined by numerous intermolecular hydrogen bonds, giving rise to a 3D network.

Thermally initiated disproportionation of manganese(II) bis(1-hydroxyethylidene)diphosphonate. Formation and properties of the lepidoid structure of manganese(II) (1-hydroxyethylidene)diphosphonate-2-hydroxyethaneaminium whiskers. Agronomical efficiency of the manganese(II) complex with (1-hydroxyethylidene)diphosphonic acid

The reaction of poorly soluble manganese(II) bis(1-hydroxyethylidene)diphosphonate tetrahydrate (Mn(H3L)2•4H2O) with 2-aminoethanol (H2NCH2CH2OH) in an aqueous medium on heating to 70—80 оС causes the initial formation of soluble manganese(II) bis(1-hydroxyethylidene)diphosphonate tris(1-hydroxyethaneaminium) (Mn(H3L)2• •3H2NCH2CH2OH•4H2O), which then disproportionates to slightly soluble manganese(II) (1-hydroxyethylidene)diphosphonate-2-hydroxyethaneaminium (MnH2L•H2NCH2CH2OH) and coordination polymer of 1-hydroxyethylidenediphosphonic acid with 2-aminoethanol containing no metal cations. In the course of the reaction, MnH2L•H2NCH2CH2OH precipitates as whiskers that are grouped into a leaf (lepidoid) structure. The latter was examined by IR spectroscopy, X-ray phase analysis, scanning electron microscopy, atomic force microscopy, optical microscopy, and thermal desorption of nitrogen. The starting and resulting manganese compounds refer to poorly soluble crystalline complexes. The presence of a 2-aminoethanol molecule in the final product leads to an increase in the solubility from 0.40 to 0.54 g in 100 mL of the solution. Poorly soluble MnH2L•H2NCH2CH2OH is easily converted to a soluble form by the treatment with 2-aminoethanol or 2-amino-2-(hydroxy- methyl)propane-1,3-diol (H2NC(CH2OH)3). The agronomical efficiency of a solution of the Mn(H3L)2•3H2NCH2CH2OH•4H2O complex was studied on the cultures of white lupine Degas, spring wheat Ester, spring rape, and pea Stabil.

Heteronuclear complexation in the system 1-hydroxyethylidenediphosphonic acid—manganese(ii)—gadolinium(iii) in aqueous solution

pH-Potentiometric method in combination with mathematical modeling was used to study the system manganese(ii)—gadolinium(iii)—1-hydroxyethylidenediphosphonic acid (HEDP, H4L). When both cations simultaneously are present in the solution, the accumulation of heteronuclear forms with the ratio of Gd: Mn: HEDP equal to 1: 1: 1, 1: 1: 2, and 1: 1: 3 was observed already in the strongly acidic pH region, while from homonuclear forms only five complexes were detected in the solution, namely, MnL26–, GdH4L2–, GdH2L+, KGd2HL2↓, and K3Gd2L2(OH)↓. It was concluded that heteronuclear complexes are much stronger and replace homonuclear forms in solution.

Действие морфолина на комплексы кобальта с (1-гидроксиэтилиден)дифосфоновой кислотой

Семенов Владимир Викторович – доктор химических наук, старший научный сотрудник, Институт металлоорганической химии им. Г.А. Разуваева Российской академии наук, 603950, г. Нижний Новгород, Бокс 445, ул. Тропинина, 49. E-mail: vvsemenov@iomc.ras.ru Золотарева Наталья Вадимовна – кандидат химических наук, научный сотрудник, Институт металлоорганической химии им. Г.А. Разуваева Российской академии наук, 603950, г. Нижний Новгород, Бокс 445, ул. Тропинина, 49. E-mail: natkamel@yandex.ru V.V. Semenov, vvsemenov@iomc.ras.ru N.V. Zolotareva, natkamel@yandex.ru G.A. Razuvaev Institute of Organometallic Chemistry of the RAS, Nizhny Novgorod, Russian Federation.

Synthesis, structure, and properties of a new Co(II) diphosphonate based on auxiliary ligand 2,2'-bipyridine

ABSTRACT The example of Co(II)-N-heterocyclic complex based on 1-hydroxyethylidenediphosphonic acid (H5L = CH3C(OH)(PO3H2)2), namely [Co2(H3L)2(2,2′-bipy)2] 1, has been solvothermally isolated using the second ligand 2,2'-bipyridine (2,2'-bipy) and characterized by powder X-ray diffraction (PXRD), elemental analysis, IR, and thermal gravimetric analyses. The single-crystal X-ray diffractions show that complex 1 possesses a 0-D structure built from binuclear unit [Co2(O–P–O)2] by μ2-(O–P–O) bridge. Then, H-bonding and π–π stacking interactions further expand this 0-D structure into a 3-D supramolecular framework. Fluorescent measurements reveal that the maximum emission peak is centered at 421.5 nm, mainly deriving from intraligand π*–π transition state of the second ligand 2,2'-bipy (λem = 419.5 nm, λex = 235 nm). Magnetism data indicate that 1 exhibits ferromagnetic behavior within binuclear Co(II) unit via μ2-(O–P–O) bridge in syn-anti mode.

Three Metal(II) Diphosphonates with d 10 Electron Configuration: Structural, Fluorescent and Electrochemical Studies

By introducing the second ligand 1,10-phenanthroline (phen), three low-dimensional examples of CdII/ZnII diphosphonates based on 1-hydroxyethylidenediphosphonic acid (H5L = CH3C(OH)(PO3H2)2), [Cd2(H3L)2(phen)2(H2O)2] 1, {[Zn3(H2L)2(phen)2]·2H2O}n 2 and [Zn2(H3L)2(phen)2]·(HOCH2CH2OH) 3, have been hydro- or solvo-thermally obtained and characterized by powder X-ray diffraction (PXRD), elemental analysis, IR, TG-SDTA. The single-crystal X-ray diffractions show that both compounds 1 and 3 display zero-dimensional structures built from binuclear units [M2(OPO)2] n (M = CdII/ZnII) via a double O–P–O bridge, and compound 2 possesses one-dimensional fish-bone inorganic chain structure with three types of coordination modes of Zn(II) ions. Then H-bond or/and π–π stacking interactions further expand the low-dimensional structures into the three-dimensional supramolecular frameworks. Fluorescent measurements reveal that the maximum emission peaks (371.5, 391.5 nm for 2 and 376.5, 392.5 nm for 3) of 2–3 have a significant increase in intensity compared to those of the phen ligand (λ em = 362.5, 379 nm, λ ex = 335 nm), which are mainly caused by intraligand π*–π emission state of the phen ligand. The results of electrochemical measurements indicate the donor ability of 1–3 has gone up, compared with the ligands (H5L and phen). Three examples of CdII/ZnII diphosphonates have been hydro- or solvo-thermally obtained. Two Zn(II) diphosphonates with 1,10-phenanthroline indicate a significant increase in intensity of fluorescence. The results of electrochemical measurements indicate the donor ability of CdII/ZnII diphosphonates increase, compared with the ligands H5L and phen.

Structural, spectral and magnetic studies of two Co(II)-N-heterocyclic diphosphonates based on multinuclear units

Two examples of Co(II)-N-heterocyclic coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L=CH3C(OH)(PO3H2)2), namely 0.5(H3NCH2CH2NH3)·[Co6(Cl2)(H3L)2(H2L)(HL)(2,2′-bipy)6] 1 and 2(NH4)·[Co3(HL)2(H2O)2(phen)2]·2(H2O) 2, have been solvothermally obtained by introducing the second ligands 2,2′-bipyridine/1,10-phenanthroline (2,2′-bipy/phen) and characterized by powder X-ray diffraction (PXRD), elemental analysis, IR, TG-DSC. The single-crystal X-ray diffractions show that compound 1 possesses a 0-D structure with hexa-nuclear cluster [Co6(O–P–O)8] built through single/double O–P–O bridges and compound 2 displays a 1-D ladder-like chain structure with magnetic topology building blocks [Co4(O–P–O)4]n. Then H-bonding and π–π stacking interactions further expand the two low-dimensional structures into three-dimensional supramolecular frameworks. Fluorescent measurements reveal that both the maximum emission peaks of 1–2 are centered at 423nm, mainly deriving from intraligand π*–π transition state of N-heterocyclic ligand 2,2′-bipy/phen, respectively. Magnetism data indicate that 1 exhibits antiferromagnetic behavior within hexa-nuclear Co(II) clusters, while 2 shows weak ferromagnetic interactions in 1-D topology Co(II)-chain, showing promising potential as magnetic materials.

Synthesis and crystal and molecular structure of three heterometallic polymeric compounds {Ln 2[LnGe6(μ-Oedph)6(μ-O)3(μ-OH)3(H2O)4] · xH2O} n [Ln = Nd, x ∼ 26 (I); Er, x ∼ 24 (II); Tm, x ∼ 20 (III); H4 Oedph = 1-hydroxyethylidenediphosphonic acid

The synthesis and X-ray diffraction study of three heterometallic compounds of general formula {Ln2[LnGe6(μ-Oedph)6(μ-O)3(μ-OH)3(H2O)4] · xH2O}n [Ln = Nd, x ∼ 26 (I); Er, x ∼ 24 (II); Tm, x ∼20 (III); H4Oedph = 1-hydroxyethylidenediphosphonic acid] are performed. The basis element of structures I–III is a hexanuclear complex anion [Ge(μ-Oedph)(μ-O)0.5(μ-OH)0.5]69−, in which bridging hydroxo and oxo ligands are statistically disordered with equally probability. Hexameric units are connected by Ln1(H2O)4 fragments into a framework whose channels are completely populated by disordered lanthanide atoms and water molecules.

Coordination compounds of oxovanadium(IV) with organophosphonic complexones in aqueous solutions

Complexation in systems containing vanadyl cations and organophosphonic acid complexone anions (POC, Pocj), such as 1-hydroxyethylidenediphosphonic acid (HEIDP, Heidp4−), nitrilotrimethylphosphonic acid (NTP, Ntp6−), and 2-phosphonobutane-1,2,4-tricarbocylic acid (PBTC, Pbtc5−), was studied by absorption spectroscopy and potentiometry. The molar and protonic compositions of the complexonates formed and the regions of their formation and existence were determined. The equilibrium constants of reactions and the stability constants of the complexonates were calculated. Experimental data were processed by the mathematical models that were able of evaluating the possibility of the existence of a wide spectrum of complex species in solution and to select the species sufficient to confirm experimental data.

Influence of Dissolved Metals and Oxidative Degradation Inhibitors on the Oxidative and Thermal Degradation of Monoethanolamine in Postcombustion CO2 Capture

In the present work, the influence of metal ions and oxidative degradation inhibitors on the stability of monoethanolamine solvents (MEA) is studied. Solvent degradation induces additional costs and impacts the environmental balance of the CO2 capture process as well as its efficiency. The two main degradation pathways of MEA are studied under accelerated conditions: oxidative degradation with continuous gas feed and thermal degradation in batch reactors. It is confirmed that metal ions (resulting from solvent impurities and wall leaching) enhance the oxidative degradation of MEA, while they do not impact its thermal degradation. Moreover, different oxidative degradation inhibitors are tested with varying results according to the inhibitor. It appears that at the selected concentration, radical scavengers like Inhibitor A and DMTD (2,5-dimercapto-1,3,4-thiadiazole) are more efficient than chelating agents like HEDP (1-hydroxyethylidene diphosphonic acid) at inhibiting oxidative degradation. Furthermore, a...

Complex formation of 1-hydroxyethylidene-1,1-diphosphonic acid with gadolinium(III) and calcium(II) in the aqueous solutions

The complex formation constant have been determined for the reactions of 1-hydroxyethylidenediphosphonic acid (H4L) with Ca(II) and Gd(III). The solubility constant has been estimated for the products differing in the ligand deprotonation state. In the cases of both cations, four complex types are common: Me(H2L)2, MeH3L2, Me2L, and Me2(HL)2. The Gd(H2L)2 and GdH3L2 complexes are much more stable than the respective calcium complexes. It has been demonstrated that, on the contrary to the commonly accepted practice, gadolinium ion cannot model the behavior of calcium ions.

A Reliable Method for Quantification of Phosphonates and Their Impurities by 31P NMR

A report of a phosphorus-31 nuclear magnetic resonance (31P-NMR) method to determine four alkylpolyphosphonates, aminotris(methylene phosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP), ethylene diamine tetra (methylene phosphonic) acid (EDTMP), and diethylenetriamine penta(methylene phosphonic) acid (DTPMP), as well as impurities (orthophosphoric acid and phosphorous acid) is described. Initially, the purity of phosphonate standards was verified. Next, calibration curves using methylphosphonic acid were built and validated. The results were compared using single point calibration. Subsequently, 24 commercial samples of phosphonates were analyzed using the two NMR methods. Concentrations determined by the two techniques were statistically equivalent. Limits of detection of 1.7, 2.4, 3.4, 2.4, 0.9, and 0.8 mg mL−1 were obtained for ATMP, HEDP, EDTMP, DTPMP, orthophosphoric acid, and phosphorous acid, respectively. 31P NMR with a single point calibration is a rapid and accurate method to analyze commercial phosphonate samples. This technique allows straightforward sample preparation and specific determination of the richness and main impurities of phosphonate samples.

Two novel Cu(II) diphosphonates: Structural, spectral and magnetic studies

By introducing the second organic N-heterocyclic ligands 2,2′-bipyridine (2,2′-bipy)/1,10-phenanthroline (phen), two mono-/bi-nuclear examples of Cu(II)-diphosphonate coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L=CH3C(OH)(PO3H2)2), [Cu(H4L)2(2,2′-bipy)]·H2O 1 and [Cu(H3L)(phen)]2·(HOCH2CH2OH)0.52, have been solvothermally obtained and characterized by powder X-ray diffraction, elemental analysis, IR, TG–DSC. The single-crystal X-ray diffractions show that both the two compounds possess zero-dimensional structures, built from mononuclear unit [CuO4N2]n for 1 and binuclear unit [–Cu–O–P–O–]2n with a double O–P–O bridge for 2 in syn-anti fashion. Then H-bond or/and π–π interactions further expand the two zero-dimensional structures into the three-dimensional supramolecular frameworks. Fluorescent measurements reveal that the maximum emission peaks of 1–2 centered at 433.5nm for 1 and 434.5nm for 2, respectively, are mainly caused by intraligand π*–π emission state of N-heterocyclic ligands (λex=235nm). The further magnetic study shows the two coordination polymers exhibit antiferromagnetic behavior for 1 between the mononuclear units, while ferromagnetic behavior for 2 derived from double O–P–O bridges in syn-anti mode between the metal centers.

Syntheses, structures and luminescent properties of two organic templated uranyl phosphonates

Two organic templated uranyl phosphonates (Hbpi)[(UO2)2(H2O)(PO3C6H5)2(HPO3C6H5)] (1) and (H2dib)0.5[UO2(H2O)(Hhedp)] (2) (bpi = 1-([1,1′-biphenyl]-4-yl)-1H-imidazole, dib = 1,4-di(1H-imidazol-1-yl)butane, H4hedp = 1-hydroxyethylidenediphosphonic acid), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR and photoluminescent spectroscopy. The structures of compounds 1 and 2 have been determined to be layered structures constructed by UO7 pentagonal bipyramids and PO3C tetrahedra of phenylphophonate and hedp groups, respectively. Adjacent layers are packed in AA stacking into the supramolecular structure, in which protonated bpi and dib molecules fill and compensate the negative charge of 1 and 2, respectively. Photoluminescence studies indicate that the two complexes exhibit characteristic green light emission of uranyl cations.