Angela Sastre

SYNTHESIS OF NOVEL UNSYMMETRICAL MONOAMINATED PHTHALOCYANINES

Abstract Metal-free monoaminophthalocyanine 3 was synthesised by reacting of subphthalocyanine 1 with 5-amino-1,3-diiminoisoindoline 2 . Alternatively, compound 3 was prepared from octadecyl-aminodiiminoisoindoline 6 by reaction with 1 to give 7 followed by acidic hydrolisis. The zinc complex 8 was obtained from 3 by treatment with anhydrous zinc acetate. The preparation of 8 by template condensation of subphthalocyanine 1 with ammodiiminoisoindoline 2 and zinc acetate was unsuccessful. In this case, a mixture of statistical distribution compounds was obtained. A tentative reaction pathway for the condensation between subphthalocyanines and diiminoisoindolines is also given.

Second harmonic generation from trinitro-substituted subphthalocyanines films: Evidence of noncentrosymmetric molecular organization

Second-harmonic generation from λ=1.06 μm fundamental light has been measured in both evaporated and spin-coated films of trinitro-substituted subphthalocyanines. Ordering of these noncentrosymmetric molecules with the dipole moment perpendicular to the film face has been achieved either by the deposition process (evaporated samples) or by corona poling (spin-coated samples). The second-order susceptibilities χ31(2)=2.36×10−9 esu (for vacuum evaporated samples) and χ31(2)=9.62×10−10–1.14×10−9 esu (for poled spin-coated samples) have been determined by comparison with an X-cut LiNbO3 crystal used as reference.

Novel tribenzhexaazaporphyrins as unsymmetric phthalocyanine analogues

The formal substitution of one isonindole subunit of a phthalocyanine by a 1,2,4-triazole moiety afforded a new family of unsymmetric azaporphyrins—of which compounds 1 and 2 are representative—with potential nonlinear optical properties.

Metallotriazolephthalocyanines as potential molecular subunits for the preparation of nonlinear optical active systems

Abstract A series of triazolephthalocyaninatonickel (II), -copper (II), and -cobalt (II) complexes have been prepared and characterized. Soluble compounds show favourable characteristics for the preparation of Langmuir-Blodgett films. Preliminary studies of their NLO properties in solution have been made.

Triazolate-containing macrocyclic transition-metal complexes derived from bis(3-aminopropyl)amine and 3,5-diacyl-1,2,4-triazoles

Template 1:1 condensation of 3,5-diacetyl- or 3,5-diformyl-1,2,4-triazole with bis(3-aminopropyl)amine in the presence of 1 equivalent of LiOH and M(ClO4)2(M = Ni, Cu, Co or Pb) produces mononuclear tetraaza 14-membered macrocyclic Schiff-base metal(II) complexes [ML]ClO4{L = 12-hydroxy-2,12-dimethyl- or 12-hydroxy-3,7,11,14,15,16-hexaazabicyclo[11.2.1]hexadeca-2,13,15-trienate}. These compounds are derived from the expected diimino macrocyclic complexes by formal addition of water across one of the azomethine bonds. Reduction of the Schiff-base complexes with sodium tetrahydroborate provides the corresponding saturated tetraaza macrocyclic complexes. Both sets of compounds were identified and studied by liquid secondary ion mass spectrometry.

Synthesis and aggregation properties of novel soluble ‘crowned’ metallotriazolehemiporphyrazines

Synthesis and preliminary studies on the aggregation and non-linear optical properties of novel, highly soluble, free and transition metal-complexed triazolehemiporphyrazines 1 containing two 15-crown-5 subunits are reported; aggregation of the ‘crowned’ metallotriazolehemiporphyrazines induced by alkali cations is observed for the first time in these kinds of compounds.

Synthesis and third-order NLO properties in LB films of triazolehemiporphyrazines

Abstract Langmuir-Blodgett (LB) films of free and cobalt(II)-metallated triazolehemiporphyrazines ( 2–4 ), including some new synthesized compounds ( 3–4 ), have been prepared and characterized. All investigated molecules adopt an edge-on arrangement in the film as previously found for the structurally related phthalocyanines (Pcs). The real and imaginary parts of the third-harmonic susceptibility χ (3) (3ω:ω,ω,ω) have been measured at 1.06 μm fundamental wavelength. Values are similar to those obtained for LB films of Pcs. No significant effects associated with cobalt metallation have been found at variance with previous results in solution at λ = 1.3 and λ = 1.9 μm.

Synthesis, magnetic and mass spectrometric studies on dinuclear complexes based on Schiff-base triazolic ligands

A series of dinuclear complexes of NiII, CoII and CuII have been prepared by template 1 : 2 condensation of 3,5-diacetyl-1,2,4-triazole and the corresponding aniline in the presence of 1 equivalent of lithium hydroxide and the corresponding metal(II) salt. The dinuclear nature of the nickel and cobalt compounds have been demonstrated by FAB mass spectrometry and magnetic measurements, which indicate the presence of antiferromagnetic exchange interactions.