Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.     

Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis

The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties.     

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

Chlorination of aromatic substrates catalyzed by the phthalocyanine complexes

The chlorination of benzene, toluene, and o-xylene with molecular chlorine in the presence of the phthalocyanine complexes of different structures was studied. The transformations of the catalysts during the reaction were investigated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1644–1647, August, 2008.     

Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers

Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10^?3 mol L^?1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation‐binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4964–4975, 2004     

Generation of highly stable amidate anion in anionic polymerization of 3‐(triethylsilyl)propyl isocyanate

To study living anionic polymerization, 3‐(triethylsilyl)propyl isocyanate (TEtSPI) monomer was synthesized by hydrosilylation of allylamine with triethylsilane and treatment of the resulting amine with triphosgene. The polymerization of TEtSPI was performed with sodium naphthalenide (Na‐Naph) as an initiator and in the absence and presence of sodium tetraphenylborate (NaBPh₄) as an additive in tetrahydrofuran (THF) at ?78 and at ?98 °C. A highly stabilized amidate anion for living polymerization of isocyanates was generated for the first time with the combined effect of the bulky substituent and the shielding action of the additive NaBPh₄, extending the living character at least up to 120 min at ?98 °C. Even the anion could exist at ?78 °C for 10 min. A block copolymer, poly(n‐hexyl isocyanate)‐b‐poly[(3‐triethylsilyl)propyl isocyanate]‐b‐poly(n‐hexyl isocyanate), was synthesized with quantitative yields and controlled molecular weights via living anionic polymerization in THF at ?78 °C for TEtSPI and ?98 °C for n‐hexyl isocyanate, respectively, with Na‐Naph with three times of NaBPh₄ as a common ion salt. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 933–940, 2004     

Synthesis and characterization of linear tetrablock quarterpolymers of styrene,isoprene, dimethylsiloxane,and 2-vinylpyridine

A series of five tetrablock quarterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine with molecular weights varying from 117 × 10³ to 177 × 10³ and having different compositions were synthesized. The synthesis was based on recent advances in the controlled high-vacuum anionic polymerization of hexamethylcyclotrisiloxane and on the selective linking of poly(dimethylsiloxane)lithium with the chlorosilane group of the heterofunctional linking agent chloromethylphenylethylene dimethylchlorosilane. Combined characterization results by size exclusion chromatography, membrane osmometry, and NMR spectroscopy suggested that the synthesized multiblock multicomponent polymers had a high degree of structural and compositional homogeneity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 514–519, 2004     

Microsolvation of phthalocyanines in superfluid helium droplets.

Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule.     

Micellar effect in hydroformylation of high olefin catalysed by water-soluble rhodium complexes associated with sulfonated diphosphines

High linear alkenes (1-octene and 1-decene) have been hydroformylated using water-soluble rhodium complexes associated with sulfonated diphosphines in the presence of ionic surfactants or methanol. In all cases, the hydroformylation activities were higher than in experiments without additives. The selectivity in aldehydes was higher when we used cetyltrimethylammonium hydrogensulfate (CTAHSO₄) as the surfactant or methanol as the co-solvent.     

Synthesis of graft copolymers with “V‐shaped” and “Y‐shaped” side chains via controlled radical and anionic polymerizations

A combination of nitroxide‐mediated radical polymerization and living anionic polymerization was used to synthesize a series of well‐defined graft (co)polymers with “V‐shaped” and “Y‐shaped” branches. The polymer main chain is a copolymer of styrene and p‐chloromethylstyrene (PS‐co‐PCMS) prepared via nitroxide‐mediated radical polymerization. The V‐shaped branches were prepared through coupling reaction of polystyrene macromonomer, carrying 1,1‐diphenylethylene terminus, with polystyryllithium or polyisoprenyllithium. The Y‐shaped branches were prepared throughfurther polymerization initiated by the V‐shaped anions. The obtained branches, carrying a living anion at the middle (V‐shaped) or at the end of the third segment (Y‐shaped), were coupled in situ with pendent benzyl chloride of PS‐co‐PCMS to form the target graft (co)polymers. The purified graft (co)polymers were analyzed by size exclusion chromatography equipped with a multiangle light scattering detector and a viscometer. The result shows that the viscosities and radii of gyration of the branched polymers are remarkably smaller than those of linear polystyrene. In addition, V‐shaped product adopts a more compact conformation in dilute solution than the Y‐shaped analogy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4013–4025, 2007