Eva M. Maya

SYNTHESIS OF ALKYNYL-LINKED PHTHALOCYANINE DYADS: PUSH - PULL HOMO- AND HETERODIMETALLIC BISPHTHALOCYANINATO COMPLEXES

Metallophthalocyanine dimers linked by butadiynyl and ethynyl bridges 3a - c and 5 a -c , respectively, have been synthesized by metal-mediated coupling methodologies. The key to the synthesis of these chromophores was the ready availability of appropriately functionalized unsymmetrical phthalocyanines 2a - c that bear a terminal ethynyl group. Following the same methodology, push - pull homo- and heterodimetallic ethynyl-bridged bisphthalocyaninato complexes 10 a - c, that contain electron-donor and electron-acceptor substituents in each of the two phthalocyanine subunits, have been also prepared.

Alkynyl substituted phthalocyanine derivatives as targets for optical limiting

One of the key issues in the development of efficient optical limiters is the search for appropriate materials with improved nonlinear absorption. Phthalocyanine materials are among the most promising nonlinear absorbers described in the literature. Ethynyl and butadiynyl-bridged bisphthalocyanines and related ethynyl-containing mononuclear compounds have been synthesized and experimentally studied using the z-scan technique with nanosecond pulses at 532 nm. We intend to ascertain the effect of the electronic interaction between macrocycles in the optical limiting performance of phthalocyanines.

Synthesis and characterization of tetraethynylphthalocyanines

Abstract Metallophthalocyanines substituted by four ethynyl groups were obtained as a regioisomeric mixture. The compounds, scarcely soluble in organic solvents, were characterized by MALDI-TOF-MS.

Palladium-heterogenized porous polyimide materials as effective and recyclable catalysts for reactions in water

New functionalized porous polyimides (PPIs-NO2, PPIs-NH2, and PPIs-NPy) were synthesized and characterized and the PPI-NPy materials were applied as supports to obtain heterogenized palladium-complexes (PPI-NPy-Pd). The PPI-NPy-Pd hybrid materials have behaved as very efficient heterogeneous catalysts in the Suzuki coupling reaction in water, affording the corresponding cross-coupling products in excellent yields. Furthermore, the catalysts have shown excellent chemical and thermal stability and good recyclability. No evidence of the leaching of Pd from the catalyst during the course of reaction was observed, suggesting true heterogeneity in our catalytic systems.

First Pre‐Functionalised Polymeric Aromatic Framework from Mononitrotetrakis(iodophenyl)methane and its Applications

Starting from mononitrotetrakis(iodophenyl)methane as monomer, we report the preparation of the first pre-functionalised porous aromatic frameworks (PAFs) and their application as supports for organometallic catalysts. Neutral coordinate imino-pyridine Schiff base (PAF-NPy) or chiral bis-amino (PAF-NPro) ligands were obtained by post-synthetic treatment of PAF-NH2 and treated with copper(I) or rhodium(I) to yield the corresponding supported transition-metal catalysts. The as-prepared PAF-NN-M catalysts exhibited activity and selectivity similar to that of the corresponding homogeneous catalysts and were easily removed from reaction media and recycled without loss of activity or selectivity.

Tetraamidometallo-phthalocyanines Langmuir-Blodgett Films: Morphology versus central metal effects on NO2 detection

Abstract Symmetrically substituted tetraamidometallo-phthalocyanines (MPc) have been deposited as Langmuir-Blodgett (LB) films onto glass substrates bearing gold interdigitated electrode patterns. CoPc, CuPc, NiPc, and ZnPc LB films were shown to possess a very high sensitivity (ΔR/R ≥ 50% at room temperature) when exposed to ppm levels of nitrogen dioxide (NO 2 ). Moreover, it has been demonstrated that the gas-sensing properties of the MPc LB films depend primarily on the nature of the central metal, and secondarily on the orientation of the macrocycle within the LB film.

Novel efficient catalysts based on imine-linked mesoporous polymers for hydrogenation and cyclopropanation reactions

Two imine-linked polymer organic frameworks (POFs) with different geometries (C3v-POF and Th-POF) and mesoporous properties were prepared and proved to be catalyst supports. Due to the greater ability of Th-POF to coordinate metals, Cu- and Ir-coordinated Th-POFs were tested as catalysts. Both act as truly heterogeneous catalysts towards cyclopropanation and hydrogenation of alkenes, respectively. The high surface area and easy accessibility to the catalytic sites make these materials very efficient for heterogeneous catalysis. The stability of the coordinated complexes and the porous frameworks allows several reuses with only a minor loss in catalytic activity.

Macroscopic third order nonlinear optical behavior of metal-containing phthalocyanines bearing alkyl-amido functional groups+

Abstract The third order susceptibilities ξ(3) Langmuir Blodgett films of two series of octasubstituted metallophthalocyanines 1 and 2 have been measured by Third Harmonic Generation (THG) experiments at 1.064 and 1.904 μm. The results indicate that the hydrogen bonding has a very weak influence in their nonlinear response. Preliminary studies in solution of tetrasubstituted metallophthalocyanines have been also performed.

Novel aromatic polyimides derived from 2,8-di(3-aminophenyl)dibenzofuran. Synthesis, characterization and evaluation of properties

Three aromatic polyimides (PIs) were prepared from a new aromatic diamine monomer derived from the rigid ring dibenzofuran. All PIs were obtained in high yield and the inherent viscosities were in the range of 0.60 and 0.74 dL g−1. Polyimides derived from 4,4′-hexafluoroisopropyliden diphthalic anhydride (6FDA) and 4,4′-(dimethylsilanediyl) diphthalic anhydride (SiDA) showed excellent solubility in a variety of aprotic polar organic solvents. All PIs showed high thermal stability with thermal decomposition temperature (TDT10%) between 555–590 °C and the glass transition temperatures (Tg) values were between 290 and 315 °C. Polymeric films were obtained from PI-6FDA and PI-SiDA solutions and then contact angle and surface free energy were tested in order to know the hydrophobicity of materials. Likewise, permeability and selectivity analyses were developed where PI-6FDA film offered a reasonably acceptable balance of permselectivity with values close to the Robeson upper-bound (1991), in particular for the CO2/CH4 gas pair.

HOMO- AND HETERO-DIMETALLIC ETHYNYL- AND BUTADIYNYL-BRIDGED BISPHTHALOCYANINATO COMPLEXES

A new type of phthalocyanine-based chromophore system having two metallophthalocyanine rings bound together through ethynyl linkages has been synthesized.