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Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)

Starting from phosphorylated allenes, a three-steps synthesis of a new class of organic azides with a 1,2-oxaphospholene carbon skeleton has been developed. The series of obtained 4-alkyl-3-azidomethyl-2-ethoxy-2,5-dihydro-5H-1,2-oxaphosphole 2-oxides were utilized in the 1,3-cycloaddition with alkyl 2-[1-(propyn-2-yl)-1H-indol-3-yl]-2-oxoacetates for the synthesis of conjugates, which are potentially active cytostatics.

Abstract Tris[2-(3′-cyanopropoxy)phenyl]phosphine oxide has been obtained via the alkylation of tris(2hydroxyphenyl)phosphine oxide with 4-bromobutyronitrile in the presence of K2CO3. The product structure has been elucidated by means of X-ray diffraction analysis. The terminal cyano groups in the obtained phosphine oxide have been converted into tetrazole rings via the click-reaction with NH4N3 to give a new hybrid tripodal propeller ligand, tris{2-[3′-(tetrazol-5′′-yl)propoxy]phenyl}phosphine oxide. Palladium(II) complexes of the prepared ligand and its short-linker analog, tris[2-(tetrazol-5′-ylmethoxy)phenyl]phosphine oxide, have been synthesized. Cytotoxicity of the ligands and their Pd(II) complexes has been studied.

Using the methodology of "click" chemistry, a series of conjugates of 3,5-bis(benzylidene)-1-(prop-2-yn)piperidin-4-ones with 4-alkyl-3-azidomethyl-2-ethoxy-2,5-dihydro-5H-1,2 oxaphosphol 2-oxides was synthesized. All newly obtained compounds 8-18 were characterized by

Extraction of lanthanides and actinides from nitric acid solutions with N-(diphenylphosphoryl)-N'-n-propylureas containing imidazolyl, diethylamino, pyrid-2-yl, 2-oxopyrrolidino fragments in the ω position of the alkyl substituent has been studied. It has been shown that Ho(III) and Yb(III) related to the yttrium subgroup of lanthanides are extracted much better than La(III) and Nd(III) related to the cerium subgroup. N-(Diphenylphosphoryl)urea containing ω-(2-oxopyrrolidino)propyl fragment at the terminal nitrogen atom shows the best extraction properties. This dependence has been theoretically explained by modeling complexation because the coordination of f-block element ion with amide oxygen atom is more preferable

The interaction of saturated acyclic α- and β-(diphenylphosphoryl)alkanones with sulfonyl- and acylhydrazines has led to the corresponding hydrazones in yield up to 90%. Structure of the obtained compounds has been elucidated using the data of single-crystal X-ray diffraction analysis and NMR spectroscopy.

New tripodal 1,2,3-triazole ligands based on triphenylphosphine oxide platform with different linker lengths have been synthesized, and their structure has been determined by elemental analysis, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and vibrational (IR and Raman) spectroscopy. The coordination and extraction properties of the new ligands have been studied in the complexation with uranyl nitrate and extraction of micro amounts of uranium(VI) from aqueous phase to 1,2-dichloroethane.

Modification of daunorubicin on its NH2 moiety is a well-established synthetic approach to obtain novel derivatives of this compound. Moreover, the daunosamine moiety of this antibiotic is considered to be the most sensitive part of a molecule in terms of biological response to chemical transformations. Using simple and effective synthetic techniques, namely, alkylation under phase-transfer catalysis and an amine addition across an activated multiple bond, a series of daunorubicin derivatives retaining the amine functionality have been obtained, which could also be used as potential precursors for further transformations.

A convenient synthesis of benzylic phosphonates and 2,3-dihydrobenzo[d][1,2]oxaphosphole 2-oxides substituted at the aromatic ring, as well as their precursors, 2-hydroxybenzylic alcohols, from the derivatives of salicylic aldehyde, salicylic acid, and 2-hydroxyacetophenone bearing an additional hydroxy or methoxy group at the para position of the aromatic ring was developed. For the first time, the possibility of selective demethylation of the methoxy group positioned ortho to the methylene phosphonate fragment with retention of the methoxy group at the para position was shown.

New hybrid tripodal propeller ligands on the triphenylphosphine oxide platform with triazole rings in the side arms and alkyl and aryl substituents in the triazole fragments have been synthesized by the click reaction. Composition and structure of the prepared compounds have been established by vibrational (IR, Raman) and multinuclear (1H, 13C, 31P) NMR spectroscopy, elemental analysis, and mass spectrometry. Coordination and extraction properties of the prepared compounds toward Pd(II) have been studied by the example of one of the ligands.

New tripodal ligand, tris(2-carbamoylmethoxyphenyl)phosphine oxide, has been synthesized via the alkylation of tris(2-hydroxyphenyl)phosphine oxide with chloroacetamide. The ligand structure has been studied by means of IR and NMR (1H, 31P) spectroscopy as well as X-ray diffraction.

New N-derivatives of daunorubicin are obtained using aromatic aldehydes by one-step reductive amination. The obtained compounds are found to exhibit a high cytotoxic activity.

A new tetrazole tripodal ligand, tris[2-(tetrazol-5-ylmethoxy)phenyl]phosphine oxide, has been obtained. Its structure in crystal and solutions has been elucidated by X-ray diffraction analysis as well as IR, Raman, and multinuclear (1H, 13C, 31P) NMR spectroscopy. Coordination properties of the polydentate ligand have been studied as exemplified by the complexation with lanthanum(III).

2,3-Bis(diphenylphosphoryl)pyridine, a novel N,O-donor bidentate organophosphorus ligand, can serve as an efficient extractant for recovery of f-block elements from nitric acid solutions.

A simple and efficient method has been proposed for the synthesis of a new N,O-donor ligand—1,2,4,5-tetrakis(diphenylphosphinyl)pyridine and complexing properties of the product with uranyl nitrate have been studied. Structure of the complex has been elucidated by means of single-crystal X-ray diffraction analysis.

A one-step method for the preparation of 3-substituted 2-(diethylphosphoryl)but-1-en-3-ynes was developed based on the reaction of phosphorylated α-allene alcohols with methanesulfonic anhydride in the presence of triethylamine. The obtained vinylacetylene derivatives are of interest as promising precursors for the creation of organophosphorus heterocyclic compounds.

A novel synthetically important reaction has been developed for the quick, convenient, and high-yield preparation of trimethylsilyl esters of phosphorus(III) acids, synthetically valuable Michaelis–Arbuzov reaction precursors. Commercially and synthetically available initial compounds used are derivatives of propan-2-ol phosphorylated in the second position capable of long-term storage and available silylating reagents: hexamethyldisilazane, bis(trimethylsilyl)acetamide, and diethyl(trimethylsilyl)amine. Also, a stepwise reaction scheme of the starting compounds with silylating reagents has been proposed.

A convenient approach to modify bioactive substrates such as daunorubicin, cytisine, and camphecene with a pentafluorosulfanylvinyl moiety have been suggested. F5S-CH = CH derivatives of da...

Based on 1,3,3,5,5-penta[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]-1-chlorocyclotriphosphazene, a series of hybrid compounds was obtained by two-step synthesis. In the molecules of the compounds obtained, hydrophobic organic residues are attached to the cyclotriphosphazene nucleus via a linker. A dialkyl substituted 1,2,3-triazole synthesized by click-chemistry methodology from acetylenic cyclotriphosphazene derivatives and organic azides in the presence of Cu(I) can be used as a linker connecting pentadioxolane-substituted phosphazene core. The reaction proceeds regioselectively with the formation of 1,4-disubstituted 1,2,3-triazoles only.

The solvent extraction of lanthanides (III) (except for Pm) from chloride medium (at μ = 0.1) into an organic phase containing 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone (HPy) and neutral tripodal ligands on the triphenylphosphine oxide platform with anchored carbamoyl side arms (2-R2NC(O)CH2OC6H4)3PO, where R = Bu (L1) and cyclo-Hex (L2) has been studied. A considerable synergistic effect (up to 107) has been observed in the presence of neutral ligands L1 or L2 in the organic phase containing HPy. The stoichiometry of the Ln(III) extracted species has been determined by slope analysis and the equilibrium constants have been calculated. It has been found that the lanthanides(III) ions are extracted with mixtures of HPy and neutral ligands L1 or L2 in toluene as LnPy3L species. The [LaPy3(H2O)2], and new [LaPy3(L1)] and [LaPy3(L2)] complexes have been synthesized and characterized via elemental analysis and IR spectroscopy. Solution structure of the above complexes has been examined by IR and multinuclear (1H, 13C, and 31P) NMR spectroscopy in toluene-d8 and CDCl3. The effect of diluents on synergistic extraction and the solution structure of mixed complexes are discussed.

The first observation of luminescence for Mn(II) complexes with a square-pyramidal geometry (C4v) of the metal is reported. The complexes of such type, namely [Mn(L)2Hal]X, where L is an O,O′-chelating ligand Me2N–CH(Ph2PO)2, Hal = Cl or Br, and X = Br, I or [MnCl4], show at ambient temperature red photoluminescence (λemmax ≈ 620 nm) with millisecond lifetimes (3.8–7.6 ms). This emission, stemming from spin-forbidden 4E(G) → 6A1(S) transitions in square-pyramidally coordinated Mn2+, is found to be responsive to temperature. Upon cooling the complexes from 300 to 77 K, the red-shift of the emission band by ≈20 nm takes place, which is accompanied by the increase of its integral intensity and lifetime. The peculiarities of the discovered Mn2+(C4v) luminescence are discussed against the classical luminescence that occurs in octahedral (Oh) and tetrahedral (Td) surroundings.

The reaction of 1,3-bis(diphenylphosphinyl)propane (dpppO 2 ) with MnI 2 , depending on the reactants ratio, affords either 1D coordination polymer, [Mn(dpppO 2 )I 2 ] n ( 1 ), or cage-like complex [Mn 2 (dpppO 2 ) 4 I 2 ]l 2 ( 2 ). Polymer 1 contains Mn(II) ions in a tetrahedral [Mn@O 2 I 2 ] arrangement, while the metal ions of 2 feature a square-pyramidal [Mn@O 4 I] geometry. At ambient temperature, 1 emits green phosphorescence (λ max = 530 nm) with unusually short lifetime being 50 µs, while 2 displays long-lived red phosphorescence with λ max = 660 nm and the lifetime of 1400 µs.

A series of precursors of novel tripodal ligands (2-XCH2CH2CH2OC6H4)3PO, where X = AcO, HO, MeSO2O, Br, N3, were synthesized by the alkylation of the starting tris(2-hydroxyphenyl)phosphine oxide with 3-bromopropyl acetate followed by hydrolysis of the resulting triacetate to triol and conversion of the latter to trimesylate. Treratment of the resulting trimesylate with LiBr or NaN3 was used to prepare the corresponding tribromo or triazido derivatives.

1-Hydroxy-3-(5,7-dimethyl-2-oxo-1,2-dihydro-1,8-naphthyridin-1-yl)propylidenebisphosphonic acid has been synthesized. The structure of the acid and its precursors synthesized for the first time, 3-(5,7-dimethyl-2-oxo-1,2-dihydro-1,8-naphthyridin-1-yl)propionic acid and the corresponding methyl ester, in the solid state and in the DMSO solution has been elucidated by means of vibrational (IR and Raman) and multinuclear (1H, 13C, and 31P) NMR spectroscopy.

The reaction of methyl- and phenylphosphonic dichlorides with phenols in the presence of anhydrous magnesium chloride as catalyst or magnesium metal as precatalyst provides a simple, efficient, and practical method of synthesis of the corresponding aryl methyl- and phenylphosphonochloridates.

Two unprecedented organic–inorganic hybrid complexes, [Mn(L)3]MnCl4 (1) and [Mn(L)3]MnBr4 (2), have been synthesized in 88–92% yields via reaction of Mn(II) halides with Ph2P(O)CH2C(O)NEt2 (L) in a 3:2 M ratio. X-ray diffraction analysis of 2 reveals that the metal ion of the [Mn(L)3]2+ cation has an octahedral geometry, while the [MnBr4]2− anion contains tetrahedrally coordinated Mn(II). At ambient temperature, the solid complexes 1 and 2 exhibit bright deep-red phosphorescence ( λ max em = 660 and 670 nm) with the lifetimes of 3–3.7 ms and photoluminescence quantum yields of 6% and 27%, respectively.

α-(1,2,3-Triazole)-substituted acetals were obtained using the click procedure. Under acid hydrolysis conditions these acetals were converted into earlier unknown stable gem-diols containing a triazole ring.

A ligand system containing three carbamoyl moieties secured onto a triphenylphosphine oxide platform (2-R2NC(O)CH2OC6H4)3PO, where R = Me (1), Bu (2), and cyclo-Hex (3) has been developed for lanthanide complexation and extraction from aqueous solutions. The influence of non-coordinating alkyl substituents at the nitrogen atoms in the carbamoyl side arms on coordination and extraction properties of tripodal ligands 1–3 was studied. Two new ligands 1 and 3 with alkyl substituents of different bulkiness were synthesized and characterized by spectroscopic methods. Single-crystal X-ray structures have been determined for ligands 1 and 2. The selected coordination chemistry of ligands 1–3 with Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The 1:1 complexes of all ligands 1–3 were synthesized and characterized via elemental analysis and IR spectroscopy; in addition, the crystal structure of the ligand 1 complex with neodymium nitrate was determined by X-ray diffraction. Solution structure of 1:1 complexes was examined by IR and multinuclear (1H, 13C, and 31P) NMR spectroscopy. A formation of 1:2 complexes with lanthanum and lutetium nitrates (IR, NMR, ESI-MS) has been examined and structure of the major components of 1:2 complexes solutions has been suggested for ligands 1–3. Preliminary extraction studies of Ln(III) (Ln = La, Nd, Eu, Lu) from 3 M NH4NO3 into 1,2-dichloroethane show that ligands 2 and 3 recover lanthanides much better than their mono analog [2-(Bu2NC(O)CH2O)-5-Et-C6H3]P(O)Ph2 and known extractant Ph2P(O)CH2C(O)NBu2.

Unprecedented organic–inorganic hybrid complexes, [Mn(L)3]MnHal4, containing both four- and hexacoordinated Mn2+ ions were synthesized by reacting MnCl2 or MnBr2 with bis(phosphine oxide) ligands (L) such as dppmO2, dppeO2, and 2,3-bis(diphenylphosphinyl)-1,3-butadiene (dppbO2). In the [Mn(L)3]2+ cation of the complexes, the Mn2+ ion features a [MnO6] octahedral coordination environment (Oh), and the [MnHal4]2− anion adopts a tetrahedral geometry (Td). These “two-in-one” complexes exhibit strong long-lived luminescence (τav = 12–15 ms at 300 K) having interesting thermochromic behavior attributed to the thermal equilibrium between two emission bands. So, in an emission spectrum of the typical complex [Mn(dppbO2)3]MnBr4, the intense “red” (ca. 620 nm) and weak “green” (ca. 520 nm) bands, originating from Mn2+ ions in Oh and Td environments, respectively, are observed. Cooling from 300 to 77 K simultaneously leads to (i) redshift of both bands by ca. 20 nm, (ii) increasing their intensities, and (iii) causing a substantial change of their integral intensity ratio from about 4 : 1 to 2 : 1. As a result, the colour of the emission changes from orange (CIE 0.56, 0.45) at 300 K to deep red (CIE 0.62, 0.39) at 77 K. This behavior was rationalized using steady-state and time-resolved fluorescent spectroscopy at various temperatures. The high photoluminescence quantum yields (up to 61% at 300 K) and fascinating dual-emissive phosphorescence coupled with high thermal stability and solubility suggest a high potential of this novel class of emissive Mn2+ complexes as promising emitters for OLED devices and potential stimuli-responsive materials.

A number of precursors of new tripodal ligands was obtained by hydroxyethylation of the starting tris(2-hydroxyphenyl)phosphine oxide, followed by conversion of the resulting tris[2-(2-hydroxyethoxy) phenyl]phosphine oxide to trimesylate. The treatment of the latter with LiBr or NaN3 afforded the corresponding tribromo and triazido derivatives.

Diphenylphosphinoylallenes containing a ClCH2 group were synthesized, and their reaction with cytisine was studied. It was shown that the reaction involves exclusives as nucleophilic substitution of chlorine in the chloromethyl group. The synthesized conjugates of cytisine with diphenylphosphinoylallene derivatives are of interest as potential agonists of nicotinic acetylcholine neuroreceptors (nAChRs).

A reaction of N-allyl-substituted aminomethylene-1,1-bisphosphonates with aromatic nitrile N-oxides was used to obtain new aminomethylenebisphosphonates with one or two 3-arylisoxazoline rings at the nitrogen atom. NMR spectroscopy studies showed that the bisphosphonates with two isoxazoline fragments in the molecule exist in solution as a mixture of two diastereomers.

One-step reductive amination of aromatic aldehydes using an anthracycline antibiotic daunorubicin resulted in the preparation of its new N-derivatives, which are of interest as potential antitumor drugs.

A series of pentaalkoxychlorocyclotriphosphazenes was synthesized. The spectral characteristics of the synthesized compounds (31Р, 1H, 13С NMR) were studied. It was shown that the complexity of the NMR spectra of pentaalkoxychlorocyclotriphosphazenes is associated with the magnetic nonequivalence of the phosphorus atoms in the triphosphazene cycle and the hydrogen and carbon atoms in the alkoxy groups on these phosphorus atoms, as well as the cis/trans isomerism of the latter groups.

The reaction of methyl- and phenyldichlorophosphonates with phenols in the presence of anhydrous magnesium chloride (catalyst) or magnesium metal (procatalyst) has been used as a simple, efficient, and industrially feasible method for the synthesis of the corresponding O-aryl alkyl(aryl)phosphonochloridates.

The synthesis of 3,5-bis(arylidene)piperidin-4-ones containing the 2-azidoethyl (azides 1a–d) or propargyl (acetylenes 2a–c) group at the nitrogen atom of the 4-piperidinone ring was described. The in vitro MTT assay for cytotoxicity of these compounds toward the human tumor cell lines PC3, HCT116, and MCF7 and the human embryonic kidney cells HEK293 revealed that N-(2-azidoethyl)-3,5-bis(3-pyridylidene)piperidin-4-one (1c) and N-propargyl-3,5- bis(benzylidene)piperidin-4-one (2a) exhibit high activity (IC50 in the range of 1–5 μmol L–1). The reaction of compounds 1a–d and 2a–c with malononitrile affords the corresponding 4H-pyrano[3,2-c]pyridines 3a–d and 4a–c devoid of cytotoxicity. This is evidence of the importance of preserving the 1,5-diaryl-3-oxo-1,4-pentadiene moiety upon the modification of 3,5-bis(arylidene)piperidin-4-ones in drug design when searching for new antitumor agents based on these compounds.

Methods have been developed for functionalizing the alkaloid cytisine via introduction of alka-1,3- and -2,3-dien-2-ylphosphonate fragments. The main pathway of the reaction of cytisine with 2-(diethoxyphosphoryl) alka-2,3-dien-1-yl methanesulfonates is nucleophilic substitution of the methanesulfonyloxy group with retention of the alkadiene skeleton. A minor reaction pathway is nucleophilic substitution with formation of alka-1,3-dien-2-ylphosphonates. Cytisine conjugates with exclusively alka-1,3-dien-2-ylphosphonate fragment have been synthesized by copper(I)-catalyzed 1,3-dipolar cycloaddition of N-(prop-2-yn-1-yl)cytisine to 3-azidoalka-1,3-dien-2-ylphosphonates.

A series of camphecene and quinolizidine alkaloid (-)-cytisine conjugates has been obtained for the first time using 'click' chemistry methodology. The cytotoxicity and virus-inhibiting activity of compounds were determined against MDCK cells and influenza virus A/Puerto Rico/8/34 (H1N1), correspondingly, in in vitro tests. Based on the results obtained, values of 50 % cytotoxic dose (CC50 ), 50 % inhibition dose (IC50 ) and selectivity index (SI) were determined for each compound. It has been shown that the antiviral activity is affected by the length and nature of linkers between cytisine and camphor units. Conjugate 13 ((1R,5S)-3-(6-{4-[(2-{(E)-[(1R,4R)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene]amino}ethoxy)methyl]-1H-1,2,3-triazol-1-yl}hexyl)-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one), which contains cytisine fragment separated from triazole ring by -C6 H12 - aliphatic linker, showed the highest activity at relatively low toxicity (CC50 =168 μmol, IC50 =8 μmol, SI=20). Its selectivity index appeared higher than that of reference compound, rimantadine. According to theoretical calculations, the antiviral activity of the lead compound 13 can be explained by its influence on the functioning of neuraminidase.

The first observation of luminescence for Mn(ii) complexes with a square-pyramidal geometry (C