Photonics of azacrown-containing styryl dye and its complexes with metal ions: 1. Triplet states

Photophysical processes in a styryl dye; an azacrown-containing analog; and its complexes with barium, lead, calcium, sodium, and silver cations have been studied by laser kinetic and luminescent spectroscopy. The participation of the triplet state in the degradation of photoexcitation energy has been established. Phosphorescence and delayed fluorescence of dyes and its complexes have been revealed found. It has been concluded that the molecules can exist in the excited TICT state.     

The flow in a planar-radial vortex chamber. 2. Vortex structure of the flow

A vortex structure of an air flow with a characteristic size of vortices comparable with the primary vortex size was observed in a vortex chamber of planar-radial geometry for the first time. The vortex component of the flow velocity along the chamber radius and its axis was calculated. Lavrent'ev Institute of Hydrodynamics, Siberian Division, Russian Academy of Sciences, Novosibirsk 630090. Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 41, No. 1, pp. 41–49, January–February, 2000.     

Subdirect products of finite groups with Hall π-subgroups

Translated fromMatematicheskie Zametki, Vol. 59, No. 2, pp. 311–314, February, 1996.     

Reversible PtII–CH3 deuteration without methane loss: metal–ligand cooperation vs. ligand-assisted PtII-protonation

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt^II(CH₃)₂, reacts with CD₃OD at 25 °C to undergo complete deuteration of Pt–CH₃ fragments in ∼5 h without loss of methane to form (dpk)Pt^II(CD₃)₂ in virtually quantitative yield. The deuteration can be reversed by dissolution in CH₃OH or CD₃OH. Kinetic analysis and isotope effects, together with support from density functional theory calculations indicate a metal–ligand cooperative mechanism wherein DPK enables Pt–CH₃ deuteration by allowing non-rate-limiting protonation of Pt^II by CD₃OD. In contrast, other model di(2-pyridyl) ligands enable rate-limiting protonation of Pt^II, resulting in non-rate-limiting C–H(D) reductive coupling. Owing to its electron-poor nature, following complete deuteration, DPK can be dissociated from the Pt^II-centre, furnishing [(CD₃)₂Pt^II(μ-SMe₂)]₂ as the perdeutero analogue of [(CH₃)₂Pt^II(μ-SMe₂)]₂, a commonly used Pt^II-precursor.

Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)Pt^II(CH₃)₂, reacts with CD₃OD at 25 °C to undergo complete deuteration of Pt–CH₃ fragments in ∼5 h without loss of methane to form (dpk)Pt^II(CD₃)₂ in virtually quantitative yield.     

Influence of metal cations on spectral characteristics of crown ether vinylogs with different terminal polar groups

Complexation of crown ether vinylogs containing different terminal polar groups with alkali and alkali-earth metal ions in solutions was studied by spectrophotometry. The hypsochromic shift of absorption band maxima in the UV-Vis absorption spectra indicates that the ligands containing the monobenzocrown ether fragments interact with metal ions. The scheme of complexation was proposed, and the stability constants of the complexes were determined. The efficiency of complexation depends on the metal cation size and the structure of the ionophoric fragment.     

Template effect in the synthesis of formyl derivatives of benzothiacrown compounds

The condensation of 3,4-bis(2-haloethoxy)benzaldehydes with acyclic α,ω-alkanedithiols in the presence of alkali metal carbonates in dry ethanol, DMF, MeCN and their mixtures with water gives formyl derivatives of benzothiacrown compounds in high yields. The best results are attained when the radius of the hydrated metal cation fits to the crown ether cavity. In the case of Cs⁺, high yields were observed for crown ethers of any size and composition; this can be explained by a specific template effect of this cation. The influence of the nature of the leaving group in 3,4-bis(2-haloethoxy)benzaldehydes was established for reactions with dithiols containing no ether oxygen atoms. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 11, pp. 1881–1886, November, 2000.     

Monitoring of temperature variation in the focal region of an ultrasonic transducer

A method for remote monitoring of temperature in the focal region of a high-intensity ultrasonic transducer is described. Results of measurements and theoretical simulation are presented. The measurements were conducted on a polymer sample with thermophysical and acoustic parameters close to the properties of a soft biological tissue. The sample was heated by a focused piezoelectric transducer with different values of radiation power. The delay of a probe pulse transmitted through the heated region perpendicularly to the axis of the intense ultrasonic beam was detected. The local character of temperature measurements was provided by focusing the probe pulse at the heated region. The application of an additional transducer installed confocally with the probing one provided an opportunity to enhance the precision of measurements. An analysis was conducted on the basis of a numerical solution of the heat conduction equation. The function of thermal sources in the heat conduction equation was calculated according to the results of measuring the pressure distribution in the focal region of the heating transducer. The experimental data obtained agree well with the results of simulation and demonstrate a fundamental possibility of using the proposed ultrasonic technique for remote temperature measurements.     

Crystallographic Approach to the [2 + 2] Photocycloaddition Topochemical Reactions of Unsaturated Compounds with Single Crystal Retention

Crystallography Reports - Based on the results of authors' studies, an approach to the analysis of [2 + 2] photocycloaddition (PCA) topochemical reactions of unsaturated compounds, occurring in...     

Formation of a Stable Cationic Hydridodimethylplatinum(IV) Complex by the Reaction of Bis(μ-dimethyl sulfido)tetramethyldiplatinum(II) with Protonated 1,4,7-Triisopropyl-1,4,7-triazacyclononane. A First Example of Oxidative N-H Addition to a Platinum(II) Complex

The complex bis(-dimethyl sulfido)tetramethyldiplatinum(II) reacts with 1,4,7-triisopropyl-1,4,7-triazacyclopropanone (L) over the course of 24 h at room temperature in THF-d ₈ to give [PtMe₂(L)] and PtMe₂(SMe₂)₂. Subsequent addition of 1 mol of trifluoromethanesulfonic acid results in immediate formation of a previously unknown stable cationic complex [PtMe₂H(L)]⁺SO₃CF₃ ^-. This product can also be prepared by oxidative addition of the N-H bond of LH⁺SO₃CF₃ ^- to the starting complex, which points to a higher basicity of the platinum atom in [PtMe₂(L)] compared with the nitrogen atom in the ligand L. The pK _a of the cationic hydride of platinum(IV) was estimated.