Copper Phthalocyanine Functionalized Single-Walled Carbon Nanotubes: Thin Films for Optical Detection.

Thin films of non-covalently hybridized single-walled carbon nanotubes (SWCNT) and tetra-substituted copper phthalocyanine (CuPcR4) molecules have been produced from their solutions in dimethylformamide (DMF). FTIR spectra revealed the 7π-7π interaction between SWCNTs and CuPcR4 molecules. DC conductivity of films of acid-treated SWCNT/CuPcR4 hybrid has increased by more than three orders of.magnitude in comparison with conductivity of CuPcR4 films. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements have shown that films obtained from the acid-treated SWCNTs/CuPcR4 hybrids demonstrated more homogenous surface which is ascribed to the highly improved solubility of the hybrid powder in DMF Using total internal reflection ellipsometry spectroscopy (TIRE), thin films of the new hybrid have been examined as an optical sensing membrane for the detection of benzo[a]pyrene in water to demonstrate the sensing properties of the hybrid.

Formation of ordered films of axially bridged aluminum phthalocyanine [(tBu)4PcAl]2O via magnetic field-induced reaction.

The µ-(oxo)bis[tetra-tert-butylphthalocyaninato] aluminum(III) [(tBu)4PcAl]2O films with the crystallites oriented preferably in one direction were obtained via chemical transformation of tetra-tert-butylsubstituted chloroaluminum(III) phthalocyanine (tBu)4PcAlCl film upon its annealing in magnetic field. A comparative analysis of the influence of post-deposition annealing process without and under applied magnetic field of 1 T, on the orientation and morphology of (tBu)4PcAlCl and [(tBu)4PcAl]2O films, has been carried out by the methods of UV-vis, Infrared and Raman spectroscopies, XRD as well as atomic force microscopy. The formation of [(tBu)4PcAl]2O films with elongated crystallites having preferential orientation was observed upon heating of the films in magnetic field while annealing without magnetic field under the same conditions does not demonstrate any effect on the structure and morphology of these films. The reasons of the sensitivity of this reaction to the presence of such magnetic field is discussed and studied by electronic paramagnetic resonance spectroscopy.

Synthesis and organic solar cell performance of BODIPY and coumarin functionalized SWCNTs or graphene oxide nanomaterials.

The synthesis and characterization of new hybrid materials based on reduced graphene oxide (rGO) or single walled carbon nanotubes (SWCNTs) covalently functionalized by 4,4'-difluoro-8-(4-propynyloxy)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) (2) or 7-(prop-2-yn-1-yloxy)-3-(3',4',5'-trimethoxyphenyl)-coumarin (4) as light harvesting groups have been described. The organic solar cell performances of these novel nanomaterials in P3HT:PCBM blends were investigated. These covalently bonded hybrid materials (reduced graphene oxide:BODIPY (GB), reduced graphene oxide:Coumarin (GC), SWCNTs:BODIPY (CB) and SWCNTs:Coumarin (CC)) were prepared by an azide-alkyne Huisgen cycloaddition (click) reaction between the azide bearing SWCNTs or rGO and terminal ethynyl functionalized BODIPY (2) or coumarin (4) derivatives. The formation of novel nanomaterials was confirmed by FT-IR, UV-Vis and Raman spectroscopies and thermogravimetric analysis. The best performance on P3HT:PCBM organic solar cells was produced by SWCNTs:Coumarin (CC) hybrids which were coated on an indium tin oxide coated polyethylene terephthalate film (ITO-PET). The reference device based on the P3HT:PCBM blend without CC showed a power conversion efficiency (PCE) of 1.16%, an FF of 35% and a short-circuit current density (Jsc) of 5.51 mA cm-2. The reference device with CC hybrids within the P3HT:PCBM blend increased the values significantly to 1.62% for PCE, 40% for FF and 6.8 mA cm-2 for Jsc.

Distribution of single-walled carbon nanotubes in pyrene containing liquid crystalline asymmetric zinc phthalocyanine matrix.

A novel pyrene containing asymmetric Zn(II) phthalocyanine (AB3 type) was synthesized and characterized by various spectroscopic techniques as well as elemental analysis. A symmetric polyoxyethylene substituted Zn(II) phthalocyanine (B4 type) derivative was also prepared in order to compare the properties and determine the effect of the pyrene group on the phthalocyanine molecule. Composites of synthesized zinc(II) phthalocyanine-single wall carbon nanotubes (ZnPc-SWCNTs) containing 1 and 2 wt% carbon nanotubes were prepared by mixing these two components in dichloromethane followed by removal of the solvent and drying under vacuum. The liquid crystalline properties of the pure compounds and their composites were investigated in comparison with symmetric polyoxyethylene substituted Zn(II) phthalocyanine (B4 type) by using polarized optical microscopy, differential scanning calorimetry and X-ray diffraction analysis. The distribution of the SWCNTs in the ordered matrix of the columnar mesophase of these derivatives was studied by the method of polarized Raman spectroscopy and scanning electron microscopy (SEM). It was shown that the nature of the mesophases was not altered in these composites. The I(V) dependencies for the films deposited onto interdigitated electrodes were measured and it was shown that the lateral conductivity tends to increase with increasing SWCNT concentration.

Synthesis, structure, and spectroscopic and magnetic properties of mesomorphic octakis(hexylthio)-substituted phthalocyanine rare-earth metal sandwich complexes.

The syntheses of new bis[octakis(hexylthio)phthalocyaninato] rare-earth metal(III) double-decker complexes [(C6S)8-Pc]2M (M = Gd(III), Dy(III), and Sm(III)) (2-4, respectively) are described. These compounds are very soluble in most common organic solvents. They have been fully characterized using elemental analysis, infrared, UV-vis spectroscopy, and mass spectrometry. The crystal structures of compounds 2-4 have been determined by X-ray diffraction on a single crystal. They are isostructural and crystallize in the monoclinic space group (space group C2/c). Their lattice constants have been determined in the following order: (2) a = 31.629(4) Angstroms, b = 32.861(4) Angstroms, c = 20.482(2) Angstroms, beta = 126.922(2) degrees, V = 17019(3) Angstroms(3); (3) a = 31.595(2) Angstroms, b = 32.816(2) Angstroms, c = 20.481(1) Angstroms, beta = 127.005(1) degrees, V = 16958(2) Angstroms(3); (4) a = 31.563(2) Angstroms, b = 32.796(2) Angstroms, c = 20.481(1) Angstroms, beta = 127.032 degrees, V = 16924(2) Angstroms(3). The magnetic properties of compounds 2-4 were studied, and it was revealed that the lanthanide ions and the radical delocalized on the two phthalocyanine rings are weakly interacting. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. These phthalocyanine derivatives form columnar-hexagonal (Col(h)) mesophases. Thin films of bis[octakis(hexylthio)phthalocyaninato] rare-earth metal(III) double-decker complexes (2-4) were prepared by a spin-coating technique. Thermally induced molecular reorganization within films of bis[octakis(hexylthio)phthalocyaninato] rare-earth metal(III) double-decker complexes (2-4) was studied by the methods of ellipsometry, UV-vis absorption spectroscopy, and atomic force microscopy. Heat treatment produces molecular ordering, which is believed to be due to stacking interaction between neighboring phthalocyanine moieties.