Polymorphie, Leitfähigkeit und Kristallstrukturen von Oxo-phthalocyaninato-titan(IV)

Abstract

Oxo-phthalocyaninato-titan(IV) (PcTiO) shows weak electrical conductivity of 5 · 10~1 0 Ω" 1 cm" 1 at room temperature. Doping of PcTiO with I 2 is accompanied by an increase of conductivity up to 5· 10" 3 Ω" 1 cm" 1 . PcTiO was found to exist in two modifications built up by monomeric complexes: Phase I crystallizes monoclinic in the space group Ρ 2 l /c with the lattice constants a = 1341.1(6) pm, b = 1323.0(3) pm, c = 1381.0(4) pm, β = 103.72(3)°, Ζ = 4. Phase II forms a triclinic structure in space group PT and an unit cell of dimensions a = 1216.6(4)pm, b = 1258.4(5)pm, c = 864.1 (3)pm, α = 96.28(3)°, β = 95.03(4)°, y = 67.86(4)°, Ζ = 2. In both modifications the Ti-atom exhibits a square pyramidal coordination with a short Ti -Ο distance of 165 pm and 163 pm, respectively. Close contacts exist between the phthalocyaninato planes of neighbouring molecules. Einleitung Phthalocyaninato-Metallkomplexe (PcM), die mit axialen Brückenliganden zu linearen Ketten verknüpft sind, können Eigenschaften eindimensionaler, elektrischer Leiter aufweisen [2, 3], Beispiele dieser eindimensionalen Leiter sind (PcMC 2 ) x und (PcM pyz)^, in denen das Acetylidion (C|") oder Pyrazin (pyz) als Brückenliganden fungieren und das Zentralatom Μ ein * 14. Mitteilung über "Synthese und Eigenschaften neuartiger eindimensionaler Leiter". 13. Mitteilung siehe [1] * * Anschrift des Korrespondenzautors: Prof. Dr. J. Strähle,

The Electronic and Non-linear Optical Properties of Oxo-titanium Phthalocyanines

“…The calculated Ti-N and Ti-O bond distances (indicated in Fig. 2) compare well with the averaged values of 2.07 and 1.64 Å respectively determined from X-ray crystallography [18].…”

A new form of hydroxyaluminum phthalocyanine by acid treatment. Characterization and photoactivity

“…Different dimeric structures are possible, with two PC macrocycle planes parallel and the Al-OH oriented in the same direction (head-to-tail) or in the opposite direction (head-to-head or tail-to-tail). Similar results were observed for trivalent metal Pc's (21,(33)(34)(35)(36). Thus, the X-ray structure determinations of single crystals of several vacuum-deposited thin film Pc's that have a trivalent or tetravalent metal at centre (e.g.…”

“…PcGaC1, PcAlCl, PcInC1, PcVO) have shown that they have the tendency to aggregate in the solid state in either a cofacial stack (head-to-tail) or in various interleaved slipped stacks (head-to-head or tail-to-tail). It was proposed that the slipped configuration, in which the two PC phases have more degree of movement than the a -or P-phases reported before for other Pc's (22,23), is responsible for the strongly red-shifted visible absorbance spectra (33)(34)(35)(36). Infrared spectroscopy has been used by a number of authors as an indicator of crystallographic phase for phthalocyanines (23,26,(37)(38)(39)(40).…”

Organic molecular beam deposition of metallophthalocyanines for opto‐electronics applications

“…The crystal structures of phase I and phase I1 TiOPc have been determined. [32] These films could be intermediate between amorphous and crystalline phase 11.…”