Self-Organized Thin Films of Hydrogen-Bonded Phthalocyanines: Characterization of Structure and Electrical Properties on Nanometer Length Scales (original) (raw)
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Association of some phthalocyanines: from solutions to thin films
Thin Solid Films, 1996
Three kinds of substituted phthalocyanines (Pc) were aggregated in binary solutions and via preparation of thin films. By optical absorption measurements in the visible region the aggregate structure was found to be greatly dependent on the kind of Pc and slightly dependent on the conditions under which the aggregate was formed. It was found also that LB films of substituted Pc are built up of molecular aggregates similar to those found in solutions.
Novel Network Polymeric Phthalocyanines: Synthesis and Characterization
Macromolecular Chemistry and Physics, 2005
New p-xylylenebis-(oxa-thia-propan) bridged metal-free and metallophthalocyanine polymers were synthesized. The metal-free phthalocyanine polymer (3) was prepared by the reaction of a tetranitrile monomer with 1, 8diazabicyclo[5.4.0]undec-7-ene (DBU) in pentanol. Ni-and Co-phthalocyanine polymers were prepared by reaction of the tetranitrile compound with the chlorides of Ni(II) and Co(II) in quinoline. Cu-and Zn-phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the acetates of Cu(II) and Zn(II) and DBU in amyl alcohol. Yellow PbO and Fe(CO) 5 were used to prepare Pband Fe-analog polymers, respectively. The Co-phthalocyanine polymer was also prepared using ethylene glycol instead of quinoline in the presence of the catalyst ammonium moly-bdate. (3) was chemically doped with iodine. The electrical conductivities of the polymeric phthalocyanines measured as gold sandwiches were found to be 10 À9 -10 À7 S Á cm À1 in a vacuum and in argon. The electrical conductivity of iodine doped metal-free phthalocyanine (3a) was found to be approximately 57 times higher than that of the undoped version. The extraction ability of (3) was also evaluated in THF using transition metal picrates, such as Ag 1þ , Hg 2þ , Pb 2þ , Cd 2þ , Cu 2þ and Zn 2þ . The extraction affinity of (3) for Ag 1þ was found to be highest in the heterogeneous phase extraction experiments. All the novel compounds were characterized using elemental analysis, UV-Vis, FT-IR, NMR and MS spectral data and DSC.
Synthesis and characterization, novel across adjacent ring formed phthalocyanine
Dalton Transactions, 2011
Novel mononuclear Zn(II) 4, Co(II) 5 and Cu(II) 6 metallophthalocyanines have been synthesized from 4,4¢(ethane-1,1-p-phenol-2,2-p-phenoxy)phthalonitrile 3, which can be obtained by the reaction of 4-nitrophthalonitrile 1 with 1,1,2,2-tetrakis(p-hydroxy-phenyl)-ethane 2. The target water-soluble derivatives of 7-9 were acquired from a boiling suspension of the compounds in aqueous 20% KOH solution. The synthesized complexes have been characterized by UV-vis, IR, 1 H NMR and MALDI-TOF-mass spectroscopies. In addition, the geometric and electronic structures of 2-6 were investigated by ab initio/DFT quantum mechanical calculations using the Gaussian 03 program with HF theory at the B3LYP/3-21G level. The redox properties of the complexes 4-6 were examined by cyclic voltammetry on platinum in DMSO/TBAP. These complexes displayed one-electron metallophthalocyanine-based and multi-electron hydroxyphenyl-based redox processes. The effect of temperature on the d.c. conductivity and impedance spectra of spin coated films of compounds were investigated at the temperatures between 300-452 K and in the frequency range of 40-105 Hz. Thermally activated conductivity dependence on temperature was observed for all compounds. A.c. results indicated that conduction mechanism can be explained by classical hopping barriers mechanism for all films.
Thin-film materials based on phthalocyanine derivatives: structure and physico-chemical properties
ITM Web of Conferences, 2019
In order to establish the effect of the molecular structure of mix-substituted phthalocyanine derivatives on its supramolecular organization in thin-films, the floating layers of three A 3 B-type phthalocyanine derivatives were obtained. Their supramolecular organization was determined and it was found that the studied compounds form homogeneous stable floating layers on the water surface. Structure parameters of floating layers depend both on the length of aliphatic substituents (R = C n H 2n+1) and the metal complexing agent. Ligands I and II form stable monolayer structures, which the layer packing periods increase with the elongation of aliphatic substituents: the lattice parameter (d) is 1.93 and 2.3 nm for ligands I (n = 6) and II (n = 8), correspondingly. During further compression of the formed monolayers, ligands I and II form stable bilayers, in which the arrangement of molecules remains similar to the structure of the previous monolayers. These bilayers contain minor inclusions of 3D aggregates. Metal complex III forms only stable monolayer (d = 2.06 nm), upon further compression of which 3Daggregates included in the monolayer are formed.
http://www.samipubco.com/page\_2404.html
Phthalocyanines (Pcs) are macrocyclic chemical compounds that have attracted a lot of attention in the last decade due to their varied properties. Over time, the extensive utilization of PCs has been justified due to their exceptional nature, with their numerous desirable qualities stemming from the straightforward and adaptable methods for altering their structure. These modifications have enabled a wide range of applications, including photodynamic therapy for cancer treatment, chemical sensing, solar cells, nonlinear optics, and, most recently, photoinitiator systems for various polymerization processes, including free radical, cationic, and controlled radical polymerizations. Pcs distinctive electrochemical, photochemical, and photophysical properties have made all of these advancements possible. Our motivation to emphasize the significance of phthalocyanines in chemical science is driven by their remarkable success story. This study commences with an exploration of the design and synthesis of Pcs tailored for specific applications, followed by a spotlight on innovative research that harnesses the diverse activation capabilities of these macrocycles to initiate various types and also describes characterization.
Dyes and Pigments, 2011
Two novel mesomorphic octakis and tetrakis (alkylthio)-substituted phthalocyanines of Pb(II) were synthesized and characterized using NMR, UVeVis, FT-IR and mass-spectrometry. The mesogenic properties of these new materials forming columnar-hexagonal mesophases were studied by differential scanning calorimetry, optical microscopy and X-ray diffraction. Visible absorption spectroscopy provided evidence of thermally induced molecular reorganization in films. IR spectroscopy and density functional theory calculations were used to study the preferential orientation of molecules relative to the substrate surface. The intense IR bands in the spectra of the lead phthalocyanines were assigned with the aid of quantum chemical computations. The observed increase in the intensity of the out-of-plane modes in the IR spectra correlate with an average preferential edge-on orientation of the molecules on the substrate surface in the film. The current-voltage characteristics of films before and after thermal treatment were also measured. The results confirmed the film ordering proposed on the basis of the IR and DFT studies.
ChemInform, 2011
This overview focuses on the design and preparation of phthalocyanines (Pcs) and covers both fundamental synthetic approaches and more applied research. Thus, different topics including, e.g., the preparation of conjugated assemblies using Pcs as synthetic building blocks, the supramolecular organization of appropriately featured Pc-molecules, and the incorporation of Pcs into dendrimers and polymers, are discussed in this chapter. The second part of the review has been devoted to more technological aspects of these compounds covering Pc-based nanostructures and Pcs as active components of functional devices.
Synthesis and characterization of new monomeric and polymeric phthalocyanines
Journal of Applied Polymer Science, 2008
Monomeric (M = 2Li or 2H) and polymeric (M = 2H, Zn, Cu, Co, or Ni), where M is metal or hydrogen, phthalocyanines were prepared by the tetramerization reaction of bisphthalonitrile monomer with appropriate materials. The electrical conductivities of the polymeric phthalocyanines, which were measured as gold sandwiches, were found to be 10−10–10−7 S/cm in vacuo and in air. The binding property of a Co-containing polymeric phthalocyanine (10) toward alkali, alkaline-earth, and some heavy cations was studied in tetrahydrofuran. The extraction affinity of 10 for K+ was found to be the highest in the heterogeneous phase extraction experiments. The disaggregation property of a Ni-containing polymeric phthalocyanine (11) was investigated with K+, Na+, and NH4+ cations. The intrinsic viscosities of all polymers were also measured by means of viscometry. All the novel compounds were characterized with elemental analysis, ultraviolet–visible, Fourier transform infrared, NMR, and mass spectrometry spectral data, and differential thermal analysis/thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008
Journal of Materials Research, 2011
Peripherally and nonperipherally tetrakisoctylthio-and tetrakisoctyloxy-substituted lead(II) phthalocyanines (PbPcs) were synthesized and characterized using elemental analysis, nuclear magnetic resonance, ultra violet-visible (UV-Vis), infrared (IR), and mass spectroscopies. The mesogenic properties of PbPcs were studied by differential scanning calorimetry, polarized optical microscopy, and x-ray diffraction. The effects of the substitution position and nature of linkage heteroatom on the liquid-crystalline properties and the orientation of the molecules were also studied. Visible absorption spectroscopy yielded an evidence of a thermally induced molecular reorganization in the films. Reflection-absorption IR spectroscopy was used to study the preferential orientation of molecules relative to the substrate surface. The intense bands in the IR spectra of the PbPcs were assigned with the aid of quantum chemical (density functional theory) computations.