Laser-Induced Electron-Transfer Processes in a Pyrene–β-Cyclodextrin Complex in Titanosilicate Systems

We have used fluorescent spectroscopy and laser flash photolysis to investigate the photonics of pyrene molecules in a pyrene–-cyclodextrin inclusion complex in various media. We have observed a protective effect of -cyclodextrin relative to solubilized pyrene molecules during quenching of fluorescence by Ti ions (or titanium dioxide particles) in mixed colloids. In the presence of a precursor of silica (a TEOS solution), the pyrene molecules react with the colloidal silica particles formed, and the reaction is accompanied by decomposition of the pyrene–-cyclodextrin inclusion complex and efficient photoionization of pyrene.     

Synthesis and structure of o-bis(2-fluoro-2,2-dinitroethyl)-nitromethyl ester of 2′-fluoro-2′, 2′-dinitroethyl-2″-fluoro-2″-nitroethylenecarboxime

Conclusions The product of conversion of O-bis(2-fluoro-2,2-dinitroethyl)nitromethylbis(2-fluoro-2,2-dinitroethyl)carboxime in methanol or ether is O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl-2-fluoro-2,2-dinitroethyl-2'-fluoro-2-nitroethylenecarboxinie, the structure of which has been established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2019–2021, September, 1987.     

Unusual condensation of propargylamine. Generation of the 1,3-di(propargylimino)propane anion coordinated to the cobalt(iii) atom

The reaction of propargylamine with the hexanuclear complex Co^II ₆(₃-OH)₂(OOCCMe₃)₁₀(HOOCCMe₃)₄ or the polymer [Co(OH)_n(OOCCMe₃)_2–n]_x under an argon atmosphere afforded the unstable paramagnetic tetramine complex Co^II(OOCCMe₃)₂(H₂NCH₂CCH)₄ (1). In air, if an excess of propargylamine is present, the latter complex is transformed into the complex Co^III(OOCCMe₃)₂(NH₂CH₂CCH)₂[²-N,N"-(HCCCH₂N=CHCHCH=N—CH₂CCH)] (2) containing a new ligand, viz., the 1,3-di(propargylimino)propane anion, which is a formal analog of the acetylacetonate anion. In contrast to propargylamine, 1,3-diaminopropane reacted with the Co^II trimethylacetate clusters in air to produce the cationic complex [Co^III{1,3-(NH₂)₂(CH₂)₃}₂(OOCCMe₃)₂]⁺OOCCMe₃ ^– (3) without entering into condensation reactions. The structures of the resulting complexes were determined by X-ray diffraction analysis.     

Cubane derivatives

The reduction of 1-bromo-9,9-ethylenedioxypentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]nonane-4-carboxylic acid (2) with lithium aluminum hydride and aluminum hydride in THF was studied. A new effective method for preparing 1-bromo-9,9-ethylenedioxypentacyclo[4.3.0.0^2,5.0^3,8.0^4,7]-non-4-ylcarbinol (1) based on reduction of2 with AlH₃ under mild conditions was developed.     

Synthesis and study of organic nitrates of heterofunctional series. 5. Synthesis of 3,3-bis(hydroxymethyl)oxetane mono- and dinitrates and 2,2-bis(hydroxymethyl)propane-1,3-diol (pentaerythritol) mono- and dinitrates

New procedures were developed for the synthesis of 3,3-bis(hydroxymethyl)oxetane dinitrate (1) by O-nitration of the corresponding glycol (3) or its mononitrate (6), which were prepared by the reactions of 2,2-bis(hydroxymethyl)propane-1,3-diol (pentaerythritol) (2) mono- (4) and dinitrates (5), respectively, with alkali. A new method was devised for the synthesis of compounds 4 and 5 by the reaction of tetraol 2 with concentrated HNO₃ in dichloroethane. The structures of compounds 1 and 6 were established by X-ray diffraction analysis.     

A new reaction of fluorodinitromethyl group

A general reaction of the transformation of the fluorodinitromethyl group into the fluoronitromethyl group by denitration upon treatment with Na₂SO₃ or KI in aqueous formaldehyde was found. A preparative method for synthesizing fluoronitroalcohols was developed on the basis of this reaction.     

Synthesis and properties of porous silica obtained by the template method

Micromesoporous samples of SiO₂ were synthesized by the sol-gel method using tetraethoxysilane as a starting reagent and 1–5 wt % cetylpyridinium chloride as a template under the conditions of preadsorption of colloid silica by polyethyleneglycol macromolecules. The adsorption and texture of the samples were studied by the low-temperature nitrogen adsorption-desorption technique. Preadsorption of silica sol was shown to affect the adsorption and capillary-condensation properties of silica. The surface area and the volume of mesopores increased at cetylpyridinium concentrations higher than 1 wt %. The micropore volume increased to a maximum. The capillary-condensation hysteresis loop of H4 type transformed into an H3 loop according to the IUPAC classification.     

Synthesis,structure, and ESR spectra of the new heteronuclear complex {Li4(VO)2[(OOC)2C(H)Bu]4(H2O)8}·H2O

The reaction of an aqueous solution of vanadyl sulfate VOSO₄·3H₂O, butylmalonic acid (H₂Bumal = C₄H₁₀(COOH)₂), and lithium carbonate at pH ～4–5 gave crystals of the complex Li₄(VO)₂(Bumal)₄(H₂O)₈]·H₂O (1). The structure of complex 1 was established by X-ray diffraction analysis. The molecule of complex 1 consists of two mononuclear bischelate dianionic units {VO(Bumal)₂(H₂O)} linked by four lithium ions to form the hexanuclear heterometallic {V₂Li₄} structure. The crystals and an ethanolic solution of compound 1 were studied by ESR spectroscopy.     

Synthesis,structure, and properties of trinuclear pivalate {Zn2Eu} complexes with N-donor ligands

New luminescent heterometallic complexes of Eu³⁺ and Zn²⁺ were synthesized: Zn₂Eu(NO₃)(Piv)₆(L)₂ (Piv is pivalate anion, L = MeCN (1), 2,3-lutidine (2), 2,2′-bpy (3)) and [Zn₂(Piv)₃(2,2′-bpy)₂][ZnEu(NO₃)₃(Piv)₃(2,2′-bpy)] (4). In the case of 2,2′-bpy, the order of mixing of the reagents ([Zn(Piv)₂] _n , Eu(NO₃)₃·6H₂O, and 2,2′-bpy) affects the composition of the final reaction product: the reaction of [Zn(Piv)₂] _n and Eu(NO₃)₃·6H₂O (in the ratio Zn : Eu = 3 : 1) in MeCN affords complex 1 and the subsequent addition of 2,2′-bpy (Zn : L = 1 : 1) affords complex 3. Complex 4 is formed in the reaction of [Zn(Piv)₂] _n and 2,2′-bpy (Zn : L = 1 : 1) in MeCN followed by the addition of Eu(NO₃)₃·6H₂O (Zn : Eu = 3 : 1). The luminescence spectra of compounds 1–4 (Zn : Eu = 3 : 1) exhibit metal-centered luminescence of Eu³⁺. The most efficient ligand-antenna is 2,2′-bpy, which is due to the optimum position of the triplet level of this ligand.     

Heteroligand complexes of Nd(III), Yb(III), and Er(III) dibenzoyl methanates with bis(5-pyridin-2-yl-1,2,4-triazol-3-yl)methane

Heteroligand coordination compounds Ln(Dbm)₂HL · nEtOH, where Ln is Nd(III), Yb(III), and Er(III); HDbm is dibenzoylmethane; H₂L is bis(5-pyridin-2-yl-1,2,4-triazol-3-yl)methane, are synthesized and studied. The complexes are studied by elemental analysis, TGA, and IR spectroscopy. The structure of complex [Nd(Dbm)₂ · HL · EtOH] · EtOH is determined by X-ray diffraction analysis. The crystals are triclinic, space group $P\bar 1$ , a = 10.2004(9), b = 11.3809(10), c = 20.9173(18) Å, α = 102.133(1)°, β = 103.568(1)°, γ = 100.306(2)°; Z = 2 (8416 reflections with I > 2σ(I), R = 0.053, Rw = 0.136). The luminescence of solid samples of the studied complexes is studied in the near-IR region.