Synthesis and characterization of heteroleptic rare earth double-decker complexes involving tetradiazepinoporphyrazine and phthalocyanine macrocycles.

Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates (BuPcLn(acac), 1a-c, Ln = Lu (a), Eu (b), La (c)) with a tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand (tBuPhDzPzH2, 2) produced sandwich compounds (tBuPhDzPz)Ln(BuPc) (3a-c), which represent the first heteroleptic double-deckers incorporating both Pc and DzPz decks. A combination of high-resolution mass spectrometry, UV-Vis/NIR, MCD, and 1H NMR spectroscopy, and square-wave voltammetry provided unambiguous characterization of target complexes 3 indicating that their spectral and electrochemical properties are generally intermediate with respect to their homoleptic relatives. Based on the data of solution-state 1H-1H NMR (COSY, NOESY) correlation spectroscopy supported by DFT calculations, a dimerization tendency of compounds 3 proportional to the Ln(iii) ion size was found. The spectroelectrochemical study of 3 and the corresponding homoleptic double-deckers revealed a pronounced tendency to aggregation of the one-electron oxidized forms of DzPz-containing double-decker complexes compared to homoleptic Pc2Ln compounds.

Using matrix-assisted ionization method for mass spectral identification of fullerene-dye conjugates.

Traditional soft ionization methods are not always suitable for mass spectral analysis of complex compounds. Factors such as laser radiation and heating resulting in fragmentations of sample molecules in the case of matrix-assisted laser desorption/ionization and difficulties in preparing suitable sample solutions in the case of electrospray ionization make it impossible to use these methods in some cases. Matrix-assisted ionization was used to analyze products of chemical synthesis involving pyropheophorbide and fullerene. Mass spectra were acquired using a simple effective modification of the Exactive Orbitrap mass spectrometer electrospray interface. Reliable identification of pyropheophorbide-fullerene dyad ions and its derivatives was carried out. An experimental comparison of a matrix-assisted ionization and an electrospray ionization technique demonstrated the significant advantage in sensitivity to the ions under study (approximately 20 times higher) of the matrix-assisted ionization method in this particular study.

Improvement of m/z accuracy for linear matrix-assisted laser desorption/ionization time-of-flight mass spectrometer.

RATIONALE: Linear matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is widely used in analytical and biomedical applications. The use of delayed extraction increases the resolution, but the roughness of the matrix crystals and the misalignment of the target plate in the order of a few micrometers cause a substantial spread in the ion TOF values and a decrease in mass accuracy. METHODS: The method of mass spectra correction based on the correlation of matrix fragment peaks in MALDI mass spectra was used. Experiments were performed using the MALDI-TOF instrument CMI-1600. SIMION 8.1 and MATLAB were used for ion motion simulations. Data analysis was done using the home-built custom-developed software and MATLAB. RESULTS: It was shown that the peak position drift in the MALDI-TOF mass spectra depends linearly on the TOF in a wide mass range. While using the linear correction of the TOF scale, an increase in m/z accuracy of more than 10 times was achieved. The mass accuracy was limited by the resolution of the fast Analog-to-Digital Converter (ADC) used. CONCLUSIONS: It is expected that the proposed method will significantly increase the dynamic range, since it becomes possible to sum up corrected individual mass spectra without a significant loss of resolution. Timescale adjusting can be used for both linear TOF instruments and reflector systems of various configurations.