Two-color resonance photoionization spectrum of nickelocene in a supersonic jet

Two-color photoionization of nickelocene molecules cooled in a supersonic jet is performed using a tunable nanosecond pulsed laser. The first stage of the multiphoton excitation is the transition from the highest occupied molecular orbital of nickelocene to the lowest Rydberg level. Conditions are found under which molecular ions (η ⁵-C₅H₅)₂Ni⁺ are the only product of the multiphoton ionization in the one-color experiment. Irradiation of an excited molecule by an intense pulse of another laser increases significantly the yield of molecular ions. The dependence of the yield of (η⁵-C₅H₅)₂Ni⁺ ions on the frequency of the second laser makes it possible to determine the adiabatic ionization potential of nickelocene as 6.138±0.012eV.     

Synthesis and investigation of titanium diselenide intercalated with ferrocene and cobaltocene

Single crystals and polycrystals of titanium diselenide TiSe₂ intercalated with ferrocene Fe(η⁵-C₅H₅)₂ and cobaltocene Co(η⁵-C₅H₅)₂ are synthesized. The magnetic susceptibility and electrical resistivity of the intercalation compounds are measured. The results obtained demonstrate that the intercalation brings about the formation of an impurity band with a temperature-dependent width.     

A study of peralkylated derivatives of bis(η6-benzene)chromium by gas-phase electronic absorption spectroscopy

The gas-phase electronic absorption spectra of (⁶-C₆R₆)₂Cr (R = Me (1) and Et (2)) reveal Rydberg structures, which disappear on going to the condensed phase. Each spectrum shows a Rydberg series converging to the ionization threshold. The first ionization potential determined as the series convergence limit is 4.662±0.008 eV for 1 and 4.667±0.019 eV for 2. The Rydberg bands are due to the transitions from the non-bonding MO 3d_z2 to the R4s and Rnp (n = 4—10) levels. The influence of methyl and ethyl substituents on the term values of the Rydberg transitions depends on the principal quantum number of the Rydberg MO.     

Two-color photoionization spectroscopy of jet-cooled nickelocene

Two-photon ionization of the nickelocene molecules cooled in a supersonic jet was performed for the first time by simultaneous excitation of (⁵–C₅H₅)2Ni with two tunable nano- second dye lasers. The one-photon transition from the HOMO to the Rydberg R4p level was used as the initial step of the multiphoton excitation. In a one-color experiment, the conditions were found for generation of the intact molecular ion, (⁵–C₅H₅)2Ni⁺, as the only ionic product of the multiphoton ionization. The use of an intense pulse of the second dye laser lead to an increase in the yield of the molecular ion.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1604–1606, August, 2004.     

The structure of fullerene films and their metallocene doping

Hexagonal close-packed (HCP) C₆₀ and C₇₀ films have been prepared by the Langmuir method and examined by electron microscopy and electron-diffraction analysis. It has been shown that the vacuum deposition of a C₆₀+C₇₀ mixture results in the formation of a film with small sized grains and a distorted C₆₀-HCP structure. The simultaneous deposition of C₆₀ and ferrocene results in the formation of a film with a changed morphology and an electron-diffraction pattern that contains a variable amount of ferrocene depending on the experimental conditions. The electron-diffraction pattern corresponds to the presence of the known molecular complex C₆₀[(C₅H₅)₂Fe]₂. The analogous simultaneous deposition of fullerene C₆₀ and cobaltocene results in the formation of a C₆₀ film stable in air and water, which contains carbon and cobalt (from the data of X-ray fluorescence, electron microscopy and microdiffraction). It has a different morphology and different diffraction patterns than pure C₆₀ films and, depending on the cobaltocene content (relative to that of fullerene), appears to be a fullerite film doped with various amounts of cobaltocenium fullende, which is an ionic compound.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1379–1383, August, 1994.The work was financially supported by the Russian Foundation for Basic Research (Projects 93-03-4676 and 93-03-18368).     

New insights into water‐soluble and water‐coordinated copper 15‐metallacrown‐5 gadolinium complexes designed for high‐field magnetic resonance imaging applications

The development of contrast agents specifically designed for high‐field magnetic resonance imaging (MRI) is required because the relaxation efficiency of classic Gd(III) contrast agents significantly decreases with increasing magnetic field strengths. With an idea of exploring the unique structure of lanthanide (Ln) 15‐MC‐5 metallacrowns, we developed a series of water‐soluble Gd(III) aqua‐complexes, bearing aminohydroxamate (glycine, α‐alanine, α‐phenylalanine and α‐tyrosine) ligands, with increasing number of water molecules directly coordinated to the Gd(III) ion: Gd(H₂O)₄[15‐MC_Cu(II)Glyha‐5](Cl)₃ ( 1 (Gd)), Gd(H₂O)₄[15‐MC_Cu(II)Alaha‐5](Cl)₃ ( 2 (Gd)), Gd(H₂O)₃[15‐MC_{Cu(II)Phalaha}‐5](Cl)₃ ( 3 (Gd)) and Gd(H₂O)₃[15‐MC_Cu(II)Tyrha‐5](Cl)₃ ( 4 (Gd)). In these systems, the Ln(III) central ion is coordinated by five oxygen donor atoms of the ligands and three or four inner‐sphere water molecules. The X‐ray crystal structure of metallacrown Ln(H₂O)_3,4[15‐MC_Cu(II)Rha‐5]³⁺ agrees with density functional theory predictions. The calculations demonstrate that the exchange of coordinated water molecules can proceed easily, resulting in increased relaxivity parameters. The longitudinal relaxivities (r₁) of 1 (Gd)– 4 (Gd) in water at ultrahigh magnetic field of 9.4 T were determined to be 11.5, 14.8, 13.9 and 12.2 mM^?1 s^?1, respectively. The ability to increase the number of Ln(III) inner‐sphere water molecules up to four, the planar metallacrown structure and the rich hydration shell due to strong hydrogen bonds between the [15‐MC‐5] moiety and bulk water molecules provide new opportunities for potential MRI applications.     

Reversible C=C Bond Activation by an Intramolecularly Coordinated Antimony(I) Compound

The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C₆H₃-2,6-(CH=NtBu)₂) with selected N-alkyl/aryl-maleimides RN(C(O)CH)₂ (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound.     

Fine Substituent Effects in Sandwich Complexes: A Threshold Ionization Study of Monosubstituted Chromium Bisarene Compounds

Mass‐analyzed threshold ionization spectra of jet‐cooled [(η⁶‐PhMe)(η⁶‐PhH)Cr] and [(η⁶‐Ph₂)(η⁶‐PhH)Cr] reveal with unprecedented accuracy the effects of methyl and phenyl groups on the electronic structure of bis(η⁶‐benzene)chromium. These “pure” substituent effects allow quantitative experimental determination of the ionization energy changes caused by the mutual substituent influence in bisarene systems. Two types of such influence have been revealed for the first time in bis(η⁶‐toluene)chromium.