V. E. Larchenko

Synthesis and characterization of sandwich‐type gadolinium and ytterbium crown ether‐substituted phthalocyanines

An original method based on metal-free ligand and lanthanide acetate direct interaction in the presence of a strong organic base (DBU) is used to prepare sandwich-type gadolinium and ytterbium crown-ether substituted phthalocyanines bis[4,5,4′,5′,4″,5″,4‴,5‴-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninato]gadolinium (ytterbium) and tris[4,5,4′,5′,4″,5″,4‴-,5‴-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninato]digadolinium (ytterbium) which are characterized by MALDI-TOF mass spectrometry and UV-vis spectroscopy.

Behavior of aluminum(III)-tetra-15-crown-5-phthalocyaninates in organic media by fluorescence and UV-visible spectroscopy

The results of a UV-vis and fluorescent spectral investigation of a tetra-15-crown-5-substituted aluminum phthalocyanine [(R4Pc)Al(OH)] (1), where (R4Pc)2- = 2,3,9,10,16,17,24,25-tetrakis(15-crown-5)phthalocyaninate-dianion, in different solvents (CHCl3, DMSO, MeOH) are reported. It was shown that compound exhibits a very strong tendency to aggregation with the formation of μ-fluoro dimer [((R4Pc)Al)2F]+ in the presence of F- in the low-donor solvent CHCl3. This complex is not emissive. The formation of two different emissive species [(R4Pc)AlF2]- and [(R4Pc)Al(OH)2]- during the reaction of 1 with anions (F- and OH- correspondently) in high-donor DMSO was established.

Electrochemical and spectral properties of tris[tetra(15-crown-5)phthalocyaninato]dilutetium(III)

Tris[tetra(15-crown-5)phthalocyaninato]dilutetium(III) (R4Pc)3Lu2, whose structure had been confirmed earlier by X-ray analysis, was further examined by physicochemical studies. The redox properties of this complex were investigated by cyclic voltammetry. The spectroelectrochemical study of this compound has been performed for the first time. Based on the results obtained and analysis of literature data, an electrochemical criterion related to double- and triple-decker structure of lanthanide phthalocyanines has been proposed. IR and 1H NMR data are also reported.

Crown-substituted Sc(III) phthalocyaninates: Synthesis and spectral properties

The scandium(III) complexes with tetra(15-crown-5)phthalocyanine [Sc(R4Pc)2]·0 (I) and Sc(R4Pc) · OAc (II) have been synthesized by condensation of Sc3+ with phthalocyanine H2R4Pc (4,5,4′,5′,4″,5″,4‴,5‴-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyanine). Compounds I and II have been characterized by spectral methods: electronic absorption spectroscopy, MALDI-TOF MS, IR spectroscopy, and 1H NMR. The redox properties of I and the photoluminescent properties of II have been studied.

Cation-Induced Dimerization of Crown-Substituted Phthalocyanines by Complexation with Rubidium Nicotinate As Revealed by X-ray Structural Data

The supramolecular dimeric complex [(μ-oxo)bis(tetra-15-crown-5-phthalocyaninato)(nicotinato)aluminum(III)]tetra(rubidium) bis(nicotinate) was prepared by addition of an excess of a methanol solution of rubidium nicotinate to a chloroform solution of the aluminum crown-phthalocyaninate, [(HO)Al(15C5)4Pc]. A single-crystal X-ray diffraction study of {[Rb4(NicAl(15C5)4Pc)2(μ-O)]2+(Nic-)2}·2.36HNic·11H2O demonstrated that two molecules of the aluminum crown-phthalocyaninate nicotinate are connected through an Al-O-Al bridge supported by sandwiching of crown ether moieties by Rb+ cations.

A Comparative Performance Evaluation of Some Novel "Green" and Traditional Antiscalants in Calcium Sulfate Scaling

A relative ability of industrial samples of four phosphorus-free polymers (polyaspartate (PASP); polyepoxysuccinate (PESA); polyacrylic acid sodium salt (PAAS); copolymer of maleic and acrylic acid (MA-AA)) and of three phosphonates (aminotris(methylenephosphonic acid), ATMP; 1-hydroxyethane-1,1-bis(phosphonic acid), HEDP; phosphonobutane-1,2,4-tricarboxylic acid, PBTC) to inhibit calcium sulfate precipitation is studied following the NACE Standard along with dynamic light scattering (DLS), scanning electron microscopy (SEM), and X-ray diffraction (XRD) technique. For the 0.5 mg·dm−3 dosage, the following efficiency ranking was found: ≫ . The isolated crystals are identified as gypsum. SEM images for PESA, PASP, PAAS, and HEDP and for a blank sample indicated the needle-like crystal morphology. Surprisingly, the least effective reagent PBTC revealed quite a different behavior, changing the morphology of gypsum crystals to an irregular shape. The DLS experiments exhibited a formation of 300 to 700 nm diameter particles with negative ζ-potential around −2 mV for all reagents. Although such ζ-potential values are not capable of providing colloidal stability, all three phosphonates demonstrate significant gypsum particles stabilization relative to a blank experiment.

CCDC 1566600: Experimental Crystal Structure Determination

Related Article: Lyudmila A. Lapkina, Vladimir E. Larchenko, Gayane A. Kirakosyan, Aslan Yu. Tsivadze, Sergey I. Troyanov, Yulia G. Gorbunova|2017|Inorg.Chem.|||doi:10.1021/acs.inorgchem.7b01983

Bridged dimeric aluminum(III) tetra-15-crown-5-phthalocyanines as precursors for creation of highly ordered polymer materials

The formation of μ-oxo and μ-fluoro dimers based on aluminum tetra-15-crown-5-phthalocyanine Al[(15C5)4PcX], X = OH, OCH3 (I) was studied by UV-Vis and 1H NMR spectroscopy. It is established that the formation of μ-oxo dimer (μ-O)[(15C5)4PcAl]2 in chloroform solution occurs upon titration of I with methanol, ethanol, and dimethylsulfoxide, as well as at the Al2O3-eluent interphase, upon an increase of the methanol concentration in chloroform and upon storage of I in the solid state. It is shown for the first time that the interaction of [(15C5)4PcAl(OH)] with tetrabutylammonium fluoride in chloroform results in the formation of stable μ-fluoro dimer of (μ-F)[(15C5)4PcAl]2+, structure of which identified based on UV-Vis, 1H NMR, and MALDI-TOF mass spectral data. Conditions for preparation of complex [(15C5)4PcAlF2]− in solutions are found, and the possibility of sequential transformations in the series of complexes [(15C5)4PcAl](OH) → [(15C5)4PcAlF2]− → (μ-F)[(15C5)4Pcal]2+ is shown.