- Cofacial Assembly of Partially Oxidized Metallomacrocycles as an Approach to Controlling Lattice Architecture in Low-Dimensional Molecular Solids. Chemical and Architectural Properties of the "Face-to-Face" Polymers n, Where M = Si, Ge, and Sn
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This contribution reports a detailed chemical, spectroscopic, and X-ray diffractometric study of the nature and structure of the cofacially joined metallomacrocyclic polymers n, where M = Si, Ge, Sn and Pc = phtalocyaninato.These materials are precursors for a new class of electrically conductive polymers.Improved syntheses of the polymers are first reported.Optical spectra are assigned within the context of a porphyrinic "four orbital" model and related to those of the corresponding M(Pc)Cl2 and M(Pc)(OH)2 monomers.The vibrational spectra of the polymers are assigned, employing data from the aforementioned monomers and 18O substitution.Identification of the M-O stretching modes allows an estimation of the polymer molecular weights as a function of polymerization procedure via an end group analysis.Degrees of polymerization obtained for typical samples are n = 120 (30) (M = Si), 70 (40) (M = Ge), 100 (40) (M = Sn).A parallel, radiotracer determination employing labeled M(Pc)(O3H)2 monomers yields results in favorable agreement.It is found that n can be substantially varied by controlling the polymerization conditions.X-ray diffraction measerements show the n polymers to be highly crystalline.An analysis of the powder X-ray diffraction data has been carried out with carefully selected model compounds and computer simulation techniques.The results are in good accord with the proposed structure consisting of parallel chains of cofacially arrayed metallomacrocycles.The simplest structures which fit the experimental data are as follows: n, orthorhombic space group Ibam, a = 13.80 (5) Angstroem, b = 27.59 (5) Angstroem, c = 6.66 (4) Angstroem, Z = 4, interplanar spacing = 3.33 (2) Angstroem, intrastack phthalocyanine staggering angle = 39 (3) deg, density (g cm-3) = 1.458 (21) (calcd), 1.432 (10) (found); n, tetragonal space group P4/m, a = 13.27 (5) Angstroem, c = 3.53 (2) Angstroem, Z = 1, interplanar spacing = 3.53 (2) Angstroem, intrastack phthalocyanine staggering angle = 0 (5) deg, density (g cm-3) = 1.609 (29) (calcd), 1.512 (19) (found), or tetragonal space group I4/m, a = 18.76 (7) Angstroem, c = 3.53 (2) Angstroem, Z = 2, intrastack phthalocyanine staggering angle = 0 (5) deg, density (g cm-3) = 1.589 (26) (calcd), 1.512 (10) (found); n, tetragonal space group P4/m, a = 12.82 (2) Angstroem, c = 3.83 (2) Angstroem, Z = 1, intrastack phthalocyanine staggering angle ca. 0 deg, density (g cm-3) = 1.712 (25) (calcd), 1.719 (10) (found).The data for the latter structure are best fit to a model where the larger size of the Sn(IV) ion induces buckling of the macrocycle skeleton.An approximate analysis of the diffraction line widths suggests that crystallite dimensions are on the order of several hundred angstroms and are not grossly anisotropic.
- Dirk, Carl W.,Inabe, Tamotsu,Schoch, Karl F.,Marks, Tobin J.
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- Examples of UV–Vis profiles use as tool for evidence of the metallophthalocyanines transformation
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The UV–Vis spectra for a set of MPcs (Mmetal, Pc?=?phthalocyanine ligand), i.e.: In(III)PcI (1), Hf(IV)PcI2Pht (Pht?=?phthalonitrile) (2), Sn(II)Pc (3), Sn(IV)PcI2 (4), and Ge(IV)PcI2 (5) have been examined in two solvents, O-donative acetylacetone, and non-coordinative benzene. The UV–Vis spectra in Hacac solution of 1,2 and 4,5 shows that the axially ligated iodine atoms are replaced by (acac)? anions of the solvent, whereas in 3 the oxygen donors of the solvent causing the auto-oxidation of Sn(II) to Sn(IV) ions and as a result the Sn(II)Pc is transformed into the Sn(IV)Pc(acac)2. The chloride complexes of the 1–5 compounds are formed at Hacac solution after acidification by hydrochloric acid, however each compound solution behaviors specifically. The UV–Vis spectra collected for the studied compounds at benzene solvent both before and after the solution acidization clearly indicate that the respective Q band character (besides 3) remains practically unchanged. The presence of the Cl? ions at the Sn(II)Pc solution in benzene results in the formation of Sn(IV)PcCl2.
- Kubiak, Ryszard,Dyrda, Gabriela,Ejsmont, Krzysztof
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- PHTHALOCYANINE PIGMENT, COLORING COMPOSITION AND COLOR FILTER
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PROBLEM TO BE SOLVED: To provide a phthalocyanine pigment that has excellent fastness (heat resistance, light fastness, solvent resistance) and, when used for a color filter or the like, is excellent in color properties (lightness) and the contrast ratio, without causing unusual matter due to association, aggregation or the like of molecules with each other even in a high temperature environment above 230°C. SOLUTION: The invention provides: a phthalocyanine pigment having a specific structure represented by general formula (1) or the like; and a coloring composition and a color filter using the phthalocyanine pigment. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0168
(2017/11/15)
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- Two isomorphous complexes: Dichloro[phthalocyaninato(2-)]tin(IV) and dichloro[phthalocyaninato(2-)]-germanium(IV)
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Isomorphous triclinic forms of dichloro[phthalocyaninato(2-)]tin(IV), [Sn(C32H16N8)Cl2], and dichloro[phthalocyaninato(2-)]germanium(IV), [Sn(C32H16N8)Cl2], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalonitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric [SnPcCl2] and [GePcCl2 [Pc is phthalocyaninate(2-)] molecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the molecules are additionally inclined. In both cases, the central Sn or Ge atom is six-coordinated by the four isoindole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal-bipyramidal structure. The arrangement of [SnPcCl2] and [GePcCl2] molecules in the crystal structure is determined mainly by intermolecular C-H...Cl, π-π and van der Waals interactions.
- Janczak, Jan,Kubiak, Ryszard
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p. m237-m240
(2007/10/03)
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