含氮芳氧基取代酞菁金属配合物光敏产生1O2

采用以2,5-二甲基呋喃(DMFU)为探针,通过气相色谱内标法测定了4种中心金属(Zn(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ))、4种取代基及α位或β位取代的28种含氮芳氧基取代酞菁金属配合物新物种光敏产生单线态氧(1O2)的速率常数。讨论了中心金属电子结构、取代基类型及取代位置对酞菁金属配合物光敏产生1O2能力的影响。结果表明,它们产生1O2的能力有很大差异:(1)相同取代基在相同位置取代情况下,中心金属为锌的酞菁配合物光敏产生1O2的能力均好于中心金属为铜、钴、镍的酞菁配合物;(2)氮杂芳氧基取代酞菁锌光敏产生1O2的速率常数显著大于相应位置氨基苯氧基取代酞菁锌的;(3)α位氮杂芳氧基取代酞菁锌光敏产生1O2的速率常数均大于相应取代基β位取代酞菁锌的。     

Aluminoxanes with acetylacetonate substituents

The reaction of tetraalkylaluminoxanes (R₄Al₂O; R  Me, Et and i-Bu) with acetylacetone (acacH) has been studied at various molar ratios. The acetylacetonate substituents were found to have a destabilizing effect on the stability of the aluminoxanes. The stability of these compounds decreases in the order: R₄Al₂O > R₃acacAl₂O > R₂(acac)₂Al₂O ? (acac)₄Al₂O.Aluminoxanes with acetylacetonate substituents undergo disproportionation, yielding aluminium trisacetylacetonate. The alkyl group also has an effect on the stability of alkylacetylacetonatoaluminoxanes, which decreases in the order i-Bu > Et > Me.     

4-Benzalpyrazolines with metallocenyl substituents

Conclusions 4-Benzal derivatives of pyrazolines that contain metallocenyl substituents in the 3 and 5 positions are described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, p. 1402, June, 1979.     

N-salicylideneamine derivatives with TEMPO substituents

Three N-salicylideneamine derivatives bearing TEMPO (2,2,6,6-tetra- methyl-1-piperidinyloxy) substituents were prepared in order to study their structure and property relationships and to investigate the possibilities of the existence of heat and/or light responsive magnetic properties. Curie-Weiss behavior with weak ferromagnetic intermolecular spin-spin interactions was observed in one of the radicals, while antiferromagnetic interactions were predominant for the other radicals and the structure-property relationships were investigated for the radical compounds from their crystal structures obtained by X-ray analyses. Preliminary results of the examination of their responses towards light and heat are also described.     

Phosphanes with bulky oligosilyl substituents

By reaction of dichloroheptasilane [(SiMe₃)₂MeSi]₂SiCl₂ with lithiumphosphanides LiPHR, the silylphosphanes [(SiMe₃)₂MeSi]₂SiClPHR with R = 2, 4, 6-tri-tert-butylphenyl ( = supermesityl, Mes1) (1) and Si(SiMe₃)₃ ( = hypersilyl, Hyp) (2) were prepared. Both compounds were characterized with X-ray diffraction, multinuclear NMR spectroscopy and elemental analysis. Compound 1 did not react with n-BuLi, but only with a large excess of tert-BuLi. Phosphasilene [(SiMe₃)₂MeSi]₂SiPMes¹ could be identified by a ³¹P NMR signal at +346 ppm. All attempts to separate it from the reaction mixture failed due to many by-products which had formed through SiSi and SiP bond cleavage. Lithiation of 2 was possible with 4.2 equiv. of tert-BuLi, and crystals of the lithiumphosphanide [(SiMe₃)₂MeSi]₂SiClPLiHyp (3) could be obtained from THF, albeit in a quality not sufficient for X-ray diffraction. All attempts to achieve LiCl elimination and formation of the phosphasilene [(SiMe₃)₂MeSi]₂SiPSi(SiMe₃)₃ failed due to the unusual stability of the lithiumphosphanide. Prolongued refluxing in toluene (110 °C) only led to complete loss of coordinated THF, and ³¹P⁷Li spin spin coupling could be observed in the ³¹P NMR spectrum (¹J_PLi = 84 Hz).Reaction of potassium phosphanide [(SiMe₃)₃Si]SiMe₃PK with SiCl₄ led to the formation of [(SiMe₃)₃Si](SiMe₃)P(SiCl₃) (4), which could be successfully characterized with X-ray diffraction and multinuclear NMR spectroscopy. SiP bond lengths vary between 218 pm (SiCl₃) and 230 pm (hypersilyl). Despite these differences, ³¹P²⁹Si coupling constants are nearly identical (92.4 Hz and 85.5 Hz, respectively).     

Unsymmetrical phthalocyanines with alkynyl substituents

The synthesis of unsymmetrically substituted metallophthalocyanines (M = Zn, Ni, Co) bearing two phenylethyl moieties and six alkythio substituents was achieved by co-cyclotetramerization of two different phthalonitrile derivatives, namely 4,5-di(hexylthio)phthalonitrile and 4,5-di(phenylethynyl)phthalonitrile in the presence of zinc, cobalt or nickel salts. In contrast to the totally alkyne substituted phthalocyanines, these partially alkyne-containing derivatives are more soluble and their Q band absorptions are red-shifted when compared with all alkylthio phthalocyanines. Electrochemical properties of the phthalocyanines were studied by cyclic voltammetry.     

Novel phthalocyanines with naphthalenic substituents

Phthalocyanines with four naphthyl-malonic ester groups on the periphery were synthesized by cyclotetramerization of 4-(1,1-dicarbethoxy-2-(1-naphthyl)-ethyl)-phthalonitrile. The new compounds were characterized by spectroscopic methods. The electronic spectra exhibit intense π–π* transitions from the naphthyl moiety together with the characteristic Q and B bands of the phthalocyanine core. The electrochemical properties of the 2,9,17,23-tetra-(1,1-(dicarbethoxy)-2-(1-naphthyl)-ethyl) phthalocyaninato copper(II) complex were studied by cyclic voltammetry.     

Two germatranes with bulky substituents

In 1‐adamantyl‐2,8,9‐trioxa‐5‐aza‐1‐germabicyclo­[3.3.3]undecane or 1‐adamantylgermatrane, [Ge(C₁₀H₁₅)(C₆H₁₂NO₃)], (I), and (2,8,9‐trioxa‐5‐aza‐1‐germabicyclo­[3.3.3]undecan‐1‐yl)methyl N‐cyclo­hexyl­carbamate or [(germatran‐1‐yl)meth­yl] N‐cyclo­hexyl­carbamate, [Ge(C₆H₁₂NO₃)(C₈H₁₄NO₂)], (II), the Ge atoms are characterized by trigonal–bypiramidal configurations. The Ge⋯N distances [2.266 (3) and 2.206 (3) Å in (I) and (II), respectively] are among the longest observed in germatranes. The significant distortion of the apical N—Ge—C angle in (II) is caused by crystal packing effects.     

Conducting Polymers: Partially Oxidized Bridge-Stacked Metallophthalocyanines

The synthesis and characterization of a novel class of polymeric phthalocyanines (Pc), (PcMX)_n (M-Al, Ga, Cr; X?F and M-Si, Ge, Sn; X?0) of exceptional thermal stability are summarized. These materials possess a linear MX backbone surrounded by a sheath of cofacial M-centered Pc rings.

(PcAlF)_n and (PcGaF)_n are sublimable (10^?3mmHg,540°C and 430°C, respectively) allowing for thin film formation. Iodine-doping leading to compositions (PcMXI_y)_n with y ranging from 0.06 to 5.5 is reported. Thermogravimetric analysis has proven useful for iodine analyses and has revealed that the order of thermal stability with regard to loss of iodine is (PcCrFI_y)_n < (PcGaFI_y)_n< (PcAlFI_y)_n

< (PcSioI_y)_n. Raman spectra point to I₃-and I₅-as the principle polyiodide species, though their relative proportions vary depending on M and doping level. Increases in the electrical conductivity by as much as 10⁹ with maximum conductivities in the range of 0.01–1 ohm^?1cm^?1 result from iodine doping. Conduction appears to be thermally activated (77–300K) with an apparent activation energy of 0.04eV. It is likely that electron transport is primarily ligand based and is metal-like in character.     

Homogeneously mixed porphyrin J-aggregates with rod-shaped nanostructures via zwitterionic self-assembly

To tailor functional nanomaterials, the co-assembly of self-assembling dyes in a homogeneous way would be a promising approach because the electronic properties can be tuned by the mixing ratio. Although porphyrins are important supramolecular building blocks with unique optical properties, a homogeneously mixed J-aggregate system of porphyrins has not been reported yet. Herein, we focused on three kinds of zwitterionic porphyrin diacids, H(4)TSPP(2-), H(4)T(5-STh)P(2-) and H(4)T(4-STh)P(2-), due to their capability to form J-aggregates with distinguished optical properties and well-defined nanostructures. In this study, we investigated the co-assembly behaviours of the zwitterionic porphyrins in aqueous solution by UV-vis and RLS, and investigated the morphology of the resultant homogeneously mixed J-aggregates by AFM. In the case of the combination of H(4)TSPP(2-) and H(4)T(5-STh)P(2-), they readily co-assemble to form homogeneously mixed J-aggregates with different types of binary excitonic bands, whereas the combination of H(4)T(4-STh)P(2-) and other porphyrins results in the dominant formation of the individual pure J-aggregates. Deposited homogeneously mixed J-aggregates of H(4)TSPP(2-) with H(4)T(5-STh)P(2-) consist of rod-shaped nanostructures, whose height changes discontinuously upon varying the mixing ratio. These results would provide new insights into the electronic properties and the nanostructure of self-assembled multicomponent materials.     

磺化酞菁金属的聚集及对催化氧化硫醇性能影响

磺化酞菁金属主要用作液化气脱硫醇过程碱液氧化再生催化剂。为研究磺化酞菁金属易于失活的影响因素,对比探讨了5种磺化酞菁金属(Fe、Co、Ni、Cu、Zn )在相同溶剂以及不同溶剂中的聚集作用,并研究了聚集对催化氧化硫醇活性的影响。结果表明,磺化酞菁金属聚集受溶剂影响较大,溶剂极性越强,聚集越严重;磺化酞菁金属溶液放置时间越长,磺化酞菁金属聚集体粒径越大;金属种类不同,对磺化酞菁金属聚集也有影响。聚集导致CoSPc、CuSPc催化氧化硫醇活性显著降低20%左右。     

Synthesis and Characterization of New Metal-free and Metallophthalocyanines Substituted with Tetrathiadiazamacrobicyclic Moieties

New metal-free (5, 8) and metallophthalocyanines (6, 9) containing four diazatetrathiamacrobicycles or crosswise-disubstituted attached with two nitro and two macrobicyclic groups were synthesized by cyclotetramerization of 7,8-dicyano-4,11,22,23-tetrathia-1,14-diazapentacyclo[12.10.10.0^5,10.0^16,21.0^26,31]tetratriconta-5,7,12,19,20,21,28,30,32-nonane (3), 8,10-dihydro-8,11-diimino-4,14,24,34,-tetrathia-1,17-diazapentacyclo[15.13.13.0^5,13.0^19,23.0^28,33]tetratriconta-5,7,12,19,20,22,28,30,32-nonaisoiminoindoline (4) or 6-nitro-1,3,3-trichloroisoindolenine (7) in the presence of the corresponding metal salt or a strong organic base. The new compounds were characterized by a combination of elemental analysis and ¹H NMR, ¹³C NMR, IR, UV–Vis and MS spectral data.     

Quino-4-cyanines with carbonyl-containing substituents

6-Carbonyl-substituted lepidines and their quaternary salts were synthesized. Quino-4-cyanines were obtained from them. The introduction of carbonyl-containing substituents substantially deepens the color of the dyes obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 943–947, July, 1984.     

Mesogenic benzothiazole derivatives with methoxy substituents

Two new mesogenic homologous series containing 6-methoxybenzothiazole ring at the terminus of the molecule, viz. 2-(4′-n-alkoxyphenylazo)-6-methoxybenzothiazoles and 2-[4′-(4″-n-alkoxy-benzoyloxy) phenylazo]-6-methoxybenzothiazoles were synthesized. In series I,n-butyloxy to n-tetradecyloxy derivatives exhibit nematic mesophase. Smectic A mesophase commences from then-dodecyl-oxy derivative as a monotropic phase and is retained up to the last member synthesized. All the members of series II exhibit enantiotropic nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related series to evaluate the effect of the benzothiazole ring and the methoxy substituent on mesomorphism. This paper was presented at the 10th National Conference on Liquid Crystals held at Bangalore during 9–11 October 2003     

Aromatic compounds with new fluorine-containing substituents

The introduction of strong electron-accepting fluorine-containing substituents into the aromatic moiety gives compounds with unique properties. Determination of the electronic nature of the grouping (R_f)₂PO in arylbis(perfluoroalkyl)-phosphine oxides has shown that this substituent is comparable with R_fSO₂, one of the most electron-accepting groups.A general principle is proposed for the construction of the new superstrong electron-accepting substituents by the replacement of oxygen atoms for trifluoromethylsulfonylimino groups. For example, when the oxygen atoms in CF₃SO and CF₃SO₂ groups are replaced by CF₃SO₂N=, new stable and even more electron-accepting substituents are formed. The grouping CF₃S(O)=NSO₂CF₃ corresponds to two nitro groups. A similar increase in electron-accepting ability is observed in groupings derived from other elements by replacement of oxygen atoms by the CF₃SO₂N= group.     

Metathesis of allylsilanes with aromatic substituents

Conclusions The feasibility was demonstrated for the efficient metathesis of phecyltolyl- and benzylallylsilanes on an alumorhenium catalyst promoted by tetrabutyltin. The metathesis of aryldimethylallylsilanes or aralkyldimethylallylsilanes is a preparative method for the synthesis of 1,4-bis(aryldimethylsilyl)-2-butenes or 1,4-bis(aralkyldimethylsilyl)-2-butenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2121–2123, September, 1984.     

Synthesis of polyanilines with polyaromatic substituents

Polyanilines containing diphenyl, terphenyl, anthracene, carbazole, and 4-n-hexylbenzene have been prepared through the interaction of polyanilines in the form of the emeraldine base with corresponding sodium salts of aromatic derivatives of vinyl ketones. The polymers have been characterized by thermogravimetry, IR spectroscopy, and ¹H NMR measurements. The emission characteristics of the polymers in N-methyl-2-pyrrolidone solution have been studied.     

Electrospun Polyacrylic Acid Polymer Fibers Functionalized with Metallophthalocyanines for Photosensitizing and Gas Sensing Applications

The photophysical and photochemical properties of tetraaminophthalocyanine complexes of lutetium and zinc covalently linked to polyacrylic acid were studied alongside those of unsubstituted zinc phthalocyanine within the same polymeric fiber matrix. All three phthalocyanines within the solid fiber matrices showed photoactivity by the generation of singlet oxygen as was observed in solution. The fluorescence behaviors of the composite fibers equally parallel those in solution. For the unsubstituted zinc phthalocyanine composite, the fiber showed fluorescence quenching on interaction with gaseous nitrogen dioxide similar to that in DMF and, thus could be a promising nanofabric material in developing optoelectronic devices that are responsive to the gas.