Antisar Rih Hlil

McGill University | McGill · Department of Chemistry

Herein, we have characterized in depth the effect of femtosecond (fs)-laser writing on various polydimethylsiloxane (PDMS)-based composites. The study combines systematic and nanoscale characterizations for the PDMS blends that include various photoinitiators (organic and inorganic agents) before and after fs-laser writing. The results exhibit that...

This study aims at identifying compounds incorporated into Polydimethylsiloxane (PDMS) which produce large refractive index change under fs laser exposition, potentially leading to optimal writing of waveguides or photonic devices in such a soft host. Germanium derivative, titania and zirconite derivatives, benzophenone (Bp), irgacure-184/500/1173...

We demonstrate waveguide inscription in an elastomeric PDMS host doped with a photosensitive mixture of a germanium derivative and benzophenone. Propagation and bend losses are reported paving the way towards ultra-tunable/flexible photonics devices and sensors.

We report the structural and optical properties of Nd:YAB (NdxY1−x Al3(BO3)4)-nanoparticle-doped PDMS elastomer films for random lasing (RL) applications. Nanoparticles with Nd ratios of x = 0.2, 0.4, 0.6, 0.8, and 1.0 were prepared and then incorporated into the PDMS elastomer to control the optical gain density and scattering center content over...

Oxyfluoride glass-ceramics (GCs) doped with lanthanides have recently attracted much attention as a novel optoelectronic material candidate for optical refrigeration. In this study, the optical properties of highly transparent (∼90 % in the near infrared region) ytterbium doped germanate and aluminosilicate oxyfluoride glass ceramics with different...

We report the structural and optical properties of Nd:YAB (Nd x Y 1−x Al 3 (BO 3 ) 4 )-nanoparticle-doped PDMS elastomer films for random lasing (RL) applications. Nanoparticles with Nd ratios of x = 0.2, 0.4, 0.6, 0.8, and 1.0 were prepared and then incorporated into the PDMS elastomer to control the optical gain density and scattering center cont...

We demonstrate a stable random laser (RL) consisting of a stretchable elastomer polymer composite containing Nd: YAB(NdxY1-xAl3B4O12) nanoparticles (where x is between 0.2, and 1.0), which can be tuned conveniently by controlling the strain by stretching.

We demonstrate photosensitization of PDMS using a germanium derivative and benzophenone (BP) as photosensitizing agents. Femtosecond laser written structure featuring high phase shift are reported, opening the way of ultra-tunable photonics devices.

This work demonstrates a new photosensitive glassy material in the form of poly-di-methyl-siloxane (PDMS) loaded with novel Ge-derivatives. A femtosecond laser is used to write directly into the bulk of pristine and Ge-modified PDMS. Raman spectroscopy is used to study the origin of the stable refractive index (RI) change induced by fs laser exposu...

In the present work, we propose a new PDMS-based composite material as a widely tunable, stretchable random laser medium. Nd: YAB (NdxY1-xAl3(BO3)4, with x = 0.8 particles were successfully incorporated within polydimethylsiloxane layers. The tunability of the RL system is explored under different pumping regimes, as well as the multi-directionalit...

We report a very stable elastomeric random laser (SERL) system composed of two stable materials: inorganic Nd: YAB nanoparticles and polydimethylsiloxane (PDMS). Lasing at a wavelength of 1064.5 nm is observed when the samples are exposed to pulsed nanosecond excitation at 808 nm or 532 nm, with long term (days) operation without degradation. Contr...

Ring‐opening metathesis polymerization (ROMP) of thioether‐derived oxanorbornene imide (M1) and its copolymerization with various cycloolefin comonomers such as cyclopentene (M2), cyclopent‐3‐en‐1‐ol (M3), cycloheptene (M4), and cyclooctene (M5) using Hoveyda–Grubbs second generation catalyst has been investigated. Polymerizations were performed at...

We have shown for the first time to our knowledge, that we can write directly in bulk of PDMS-RTV supported with different loading of novel photosensitive derivatives. • In this research, we have developed and studied a novel parameter for fabrication of the waveguides using a simple and facile route. • This advance will allow novel photonics funct...

This paper reports the efficient synthesis of the first class of polyisobutylene(PIB)-supported palladium-PEPPSI precatalyst (PEPPSI = pyridine-enhanced precatalyst preparation, stabilization, and initiation). The new complexes are employed in Buchwald–Hartwig amination of aryl chlorides and are found to be reasonably active in the titled cross-cou...

Linear trans-polypentenamers are highly desired materials among synthetic tire additives due to their comparable physical properties to natural rubber. trans-Polypentenamer can be prepared by equilibrium ring-opening metathesis polymerization (ROMP) using well-defined ruthenium catalyst systems. This unique feature of the equilibrium polymerization...

Ruthenium catalyzed ring closing metathesis (RCM) and ring opening metathesis polymerization (ROMP) reactions using a supported bis(arylimino)acenaphthene N-heterocyclic carbene (BIAN-NHC) complex have been reported. The BIAN-NHC Ru-complex exhibits excellent catalytic activity and tolerates a wide range of substrates at low catalyst loadings. DFT...

Linear trans-polypentenamers are highly desired materials among the synthetic tire additives due to their comparable physical properties to natural rubber. Trans-polypentenamer can be prepared by equilibrium ring-opening metathesis polymerization (ROMP) using well-defined ruthenium catalyst systems. This unique feature of the equilibrium polymeriza...

In the past decade, numerous examples of chemical technologies based on olefin metathesis have been developed to make olefin metathesis increasingly dominant in several sustainable and green chemical processes. In spite of the wide application profile, conjugated olefin metathesis, especially conjugated polyene metathesis, is an area of great inter...

N-Heterocyclic Carbenes (NHCs): Over the last two decades N-Heterocyclic carbenes (NHCs) have immensely attracted chemists in nearly all fields of chemistry. N-Heterocyclic carbenes are commonly encountered in coordination chemistry, they are extensively used as ligands for organometallic complexes. Perhaps the biggest hit of NHCs ligands was their...

The title catalyst (H2IMes)[3,5-NC5H3(CH2CH2Rf8)2]2(Cl)2Ru(=CHPh) [H2IMes=1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene, Rf8=(CF2)7CF3] was prepared from the fluorous pyridine 3,5-NC5H3(CH2CH2Rf8)2 (2.1equiv.) and the pyridine complex (H2IMes)(NC5H5)2(Cl)2Ru(=CHPh). 3,5-NC5H3(CH2CH2Rf8)2 was synthesized by a Heck reaction of 3,5-dibr...

Polymers and copolymers containing 1H-benzo[d]imidazol-2(3H)-one units have been synthesized under conditions generally used for the synthesis of poly(aryl ether)s. 1H- benzo[d]imidazol-2(3H)-one behaves like a biphenol in the polymerization reaction. The soluble homopolymer has a very high glass transition temperature (348° C.), good thermal sta...

Novel homopolymers and copolymers containing 2H-benzimidazol-2-one units have been synthesized by N–C coupling reactions of 1H-benzo[d]imidazol-2(3H)-one and activated aromatic dihalides under conditions similar to those for the synthesis of poly(aryl ether)s and poly(benzimidazole sulfone)s. 1H-Benzo[d]imidazol-2(3H)-one behaved like a bisphenol i...

A novel difluoride containing carbazole groups was designed. Two series of polycarbazoles based on the novel monomer were synthesized via C-N coupling reactions with either 4,4′-biphenol or bisphenol A. Copolymers were obtained with 4,4′-difluorobenzophenone or bis(4-fluorophenyl) sulfone as comonomer. The solubilities of the poly(carbazole ketones...

3-(4-Fluorobenzoyl)carbazole was synthesized by a Friedel-Crafts reaction of carbazole with 4-fluorobenzoylchloride. H-NMR and MALDI-TOF MS confirmed the structure and the purity. Copolymers of these NH/OH-containing monomers were prepared with 4, 4′-biphenol and bis(4-fluorophenyl)sulfone as comonomers by combined C-O and C-N coupling reactions wi...

The synthesis and properties of the first examples of dendritic multiblock coPESs, bearing sulfonated dendritic clusters, that form strong membranes are described. End-capped dendritic multiblock coPESs with various average block lengths (n = 50–80) were synthesized by two-step reactions. The synthesis of dendritic blocks consisting of difunctional...

1,3-Phthaloyl bis-9H-carbazole (MPC) and 1,4-phthaloyl bis-9H-carbazole (PPC) were synthesized by a Friedel-Crafts reaction of carbazole with terephthaloyl chloride or isophthaloyl chloride. Homopolymers were obtained by a CN coupling reaction with activated difluorides and copolymers were synthesized with 4,4′-biphenol as a comonomer by a nucleoph...

A novel series of benzimidazole-containing sulfonated poly(arylene sulfones)s with controllable amount of basic 2,6-bis(benzimidazol-2-yl)pyridine (BIP) and sulfonic acid groups have been prepared by the copolycondensation of a new BIP-containing arylene difluoride monomer (DFSBIP) with a sulfonated arylene difluoride (DSDFS) and 4,4′-biphenol (BP)...

Multiblock copoly(ether-sulfone)s (PESs) bearing anchor units for the construction of dendritic blocks were synthesized by two-step reactions: (1) synthesis of PES block with both phenoxide end-groups; (2) chain extension and end-capping of the block by use of excess novel hexafunctional agent, hexakis(4-(4-fluorophenylsulfonyl)phenyl)benzene. The...

A study was conducted, to demonstrate the effect of branched polyether ketones with 3,6-Ditrityl-9H-Carbazole end-groups on ionomers for proton exchange membrane fuel cells. The end-groups were synthesized with an aromatic electrophilic substitution reaction of 9H-carbazole, with trityl chloride, by heating at 220-230 °C for 0.7 hours. The study al...

Polymers and copolymers of formula I: Figure US07696298-20100413-C00001 in which m is typically 30 to 500 and n is 0 to 500; Ar is for example, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, or 2,6-pyridylene; Ar2 and Ar3 are selected from various bivalent aryl and heteroaryl groups; and X is for example, the bivalent SO2 or CO. have high temperatur...

Poly(arylene ether benzimidazole) was synthesized by the reaction of biphenls containing benzimidazole moieties with activated halides. Poly(arylene ether) containing N-arylenebenzimidazole groups were also prepared by the aromatic nucleophilic displacement reaction of bis(4-hydroxyphenyl-N- arylenebenzimidazole) with activated aromatic difluorides...

High molecular weight poly(phthalazinone ether)s were synthesized by Ullmann C-N and C-O condensation reaction. 1,2-dihydro-4-(4-hydroxyphenyl)-1- (2H)-pthalazinone and unactivated aromatic dibromides were catalyzed by cuprous chloride and quinoline as ligand. Higher polymerization temperature facilitated the formation of higher molecular weight po...

The first examples of branched wholely aromatic polyether ketones (PEK) bearing clusters of sulfonic acid groups only on the end groups are presented. The novel trifunctional branching agent, 1,3,5-tris(4-(4-fluorophenylsulfonyl) phenyl)benzene was synthesized by Friedel-Crafts reaction of 1,3,5-triphenylbenzene with 4-fluorobenzenesulfonyl chlorid...

The first examples of branched wholely aromatic polymers polyether ketones (PEK) bearing clusters of sulfonic acid groups only on the end groups are presented. The key end group with pensant phenyl group as selective post-sulfonation sites, 1-(4-Hydroxyphenyl)-2,3,4,5,6-pentaphenylbenzene was successfully synthesized via Diels-Alder reaction of 1-m...

The preparation of bicarbazole-based high-performance polymers such as copoly (arlene bicarbazole)s by a nucleophilic substitution polycondensation reaction was reported. The evaporation of cresol from a solution of the homopoly(arylene bicarbazole) gives flexible and opaque films. The film forming ability of the homo(arylene bicarbazole) indicates...

Analysis of X-ray powder data for the melt-crystallisable aromatic poly(thioether thioether ketone) [–S–Ar–S–Ar–CO–Ar]n, (‘PTTK’, Ar=1,4-phenylene), reveals that it adopts a crystal structure very different from that established for its ether-analogue PEEK. Molecular modelling and diffraction-simulation studies of PTTK show that the structure of th...

2,3-Bis(4-fluorobenzoyl)naphthalene was synthesized, and poly(aryl ether)s were prepared through a reaction with various bisphenols in the solvent N,N-dimethylacetamide in the presence of potassium carbonate. Through a reaction with hydrazine or benzylamine, the corresponding benzo[g]phthalazine or benz[g]isoquinoline was formed. The conversion int...

The convenient synthesis of (3-(4-tert-Butylphenyl)-4-phenyl-5-(4′-diphenylaminostilben-4-yl)-1,2,4-triazole) is described. This molecule, labeled TAZ-TPA is composed of triphenylamine (known to transport holes) and triazole (known to transport electrons) moieties. TAZ-TPA is easily obtained as a thin solid film by vacuum evaporation. Devices made...

High molecular weight phthalazinone containing poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s with very high glass transition temperatures were synthesized from a series of new bisphthalazinone monomers. Bisphthalazinone monomers 7a-c and 8c were synthesized from 2-(4-chlorobenzoyl)benzoic acid in high yields. Poly(aryle...

Three new phenyl-substituted tris(8-hydroxyquinoline)aluminum (AlQ3) derivatives have been synthesized: tris(5-phenyl-8-quinolinolate-N1,O8)aluminum, tris(5,7-diphenyl-8-quinolinolate-N1,O8)aluminum, and tris[5,7-bis(p-fluorophenyl)-8-quinolinolate-N1,O8]aluminum. These AlQ3 derivatives are easily soluble in common organic solvents and form solid-p...

High-molecular-weight poly(phthalazinone)s with very high glass-transition temperatures (Tg's) were synthesized via a novel N–C coupling reaction. New bisphthalazinone monomers (7a–e) were synthesized from 2-(4-chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34–0.91 dL/g, were prepared...

This study focused on understanding the strong adhesion between coatings, up to 20 μm thick, made from a pyrolyzed polymer (M2-48) and a stainless steel plate (316L). Using X-ray diffraction, no carbide phase was detected in the coating. However, iron was detected by Rutherford backscattering spectroscopy throughout the entire thickness of the carb...

The synthesis and characterization of new monomers and polymers containing the 1,2,4-triazole group are described. A model reaction of 4-N-amino-3,5-diphenyltriazole with phthalic and naphthalic anhydride demonstrated the preparation of the 1,2,4-triazole-imide compounds containing a N−N linkage. From 4-amino-3,5-bis(4-hydroxyphenyl)triazole four n...

B1553, a functionalized derivative of isobenzofuran is highly fluorescent in solution in toluene but also in the solid state, where its emission peaks at 508nm. B1553 is able to transport electrons and holes but is, however, a better electron transport (ET) than a hole transport material. It is possible to use B1553, vacuum sublimed or spin-coated...

Double spin-coated electroluminescent (EL) devices have been prepared by combining a blue EL arylamine-based hole transport polymer (STPD-QP) in the first spin-coated layer with a blue EL oxadiazole-based electron transport polymer (SP-OX) in the second layer. The luminance and efficiency of these devices are improved by adding PBD, a low molecular...

High carbon content polymers have been synthesized and pyrolyzed between 600 and 850°C in inert ambient, during various pyrolysis times, to obtain freestanding carbon films with specific resistivities that can be as low as Ω cm. One of these polymers (M2-48), with a low specific resistivity at low pyrolysis temperature and pyrolysis time, can be...

Four new bisphenols containing 3,6-dialkoxyphthalimide moieties were prepared in high yields. They were copolymerized with BPA or 2,5-bis(4-hydroxyphenyl)oxadiazole by reaction with decafluorobiphenyl and with NaH as base to give novel copoly(arylene ether)s. The resulting copolymers have glass-transition temperatures (Tg) ranging from 153 to 235°C...

Three novel conjugated biphenols 3, 4, and 8 were synthesized by the Pd(OAc)2-catalyzed regioselective carbon−carbon coupling reaction of 2,6-di-tert-butylphenol or 2-phenylphenol with aryl halides. Although poly(arylene ether)s derived from biphenol 3 and arylene difluorides have low solubility in organic solvents, using 4,4‘-(9-fluorenylidene)dip...

High molecular weight aromatic polyformals free of macrocyclic oligomers were synthesized using condensative chain polymerization reaction. The reaction of bisphenol with methylene bromide in the presence of potassium hydroxide in a solvent like N-methylpyrrolidinone was carried out under high-intensity mixing conditions at about 100° centigrade. T...

The synthesis of a novel biphenol from phenolphthalein that contains an anhydride group is described. The biphenol readily undergoes further reactions. Two biphenols that contain the 1,2-benzoylenebisbenzimidazole or phthaloperin-12-one moiety, respectively, were prepared from the biphenol anhydride by reaction with aromatic diamines, o-phenylenedi...

In this article, the synthesis of a tris(8-hydroxyquinoline)aluminum (AlQ3)-containing poly(arylene ether) (4) is reported. The presence of AlQ3 pendants in polymer 4 is confirmed by NMR, ultraviolet–visible, photoluminescence, and gel permeation chromatography analyses. This is the first report of the attachment of AlQ3 complexes as side chains to...

In this article, the synthesis of a tris(8-hydroxyquinoline)aluminum (AlQ3)-containing poly(arylene ether) (4) is reported. The presence of AlQ3 pendants in polymer 4 is confirmed by NMR, ultraviolet–visible, photoluminescence, and gel permeation chromatography analyses. This is the first report of the attachment of AlQ3 complexes as side chains to...

The design and synthesis of novel charge (hole- or electron-) transport materials have been the focus of much research in recent years because of their wide variety of applications. In this study, three high molecular weight poly(arylene ether)s, 6a–c, containing naphthyl-substituted benzidine moieties have been synthesized from carbamates derived...

Novel poly(arylene ether)s were synthesized from new biphenol monomers 14–161 containing imido- or dicyanoarylene groups. The syntheses of these polymers were carried out in tetramethylene sulfone in the presence of anhydrous K2CO3, by a nucleophilic substitution condensation between the biphenol and activated difluoro compounds to give high molecu...

New electroluminescent (EL) molecules, dissolved in a high T gpoly(aryl-ketone) (A435), have been used in double spin-coated electroluminescent devices. The first EL molecule is a soluble AlQ3 derivative and the second one is a hexaphenyl-substituted isobenzofuran. The maximum solubility of both EL molecules in A435 is about 70 wt%. The typical str...

A highly substituted and fluorescent Isoindole has been used in a bilayer type of organic electroluminescent device with either PVK or Alq3. The best results (maximum luminance >6000 cd/m2, apparent quantum yield at max luminance of 1.1%, and a low threshold voltage of 4 V) are obtained for the combination: anode/Isoindole/Alq3/cathode. These devic...

A luminescent bipolar polymer 7, consisting of a Ar3N−stilbene moiety and an oxadiazole moiety, has been synthesized. A smooth and dense thin film of polymer 7 is easily obtained by spin-coating from its chloroform solution. This film exhibits a strong fluorescence in the blue. More importantly, polymer 7 possesses an extremely high thermal stabili...

A series of novel poly(arylene ether ketone)s were synthesized from the reaction of hydroquinone and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one with 4,4′-difluorobenzophenone in N-cyclohexylpyrrolidinone containing anhydrous potassium carbonate. The polymers exhibited high glass transition temperatures together with excellent thermooxidative stabilit...

TPD has been dissolved in A435, a high Tg host polymer, in order to inhibit the crystallization of the hole transport molecule. Solid solutions of TPD have been obtained for a TPD content, x, ranging from 25 to 90 wt%. A435 + x TPD films coated onto ITO are stable during at least 72h at 150°C, for TPD contents of 50 wt% and below. OLEDs having the...

One-pot polymerization between bis(N,N‘-dimethyl-S-carbamate)s and activated dihalo compounds was extended to the synthesis of semicrystalline poly(arylene thioether)s as well as their copolymers. Aromatic poly(thioether thioether ketone) (PTTK) and poly(thioether biphenyl thioether ketone) (PTBTK) were synthesized from 4,4‘-difluorobenzophenone an...

Novel poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s were synthesized from the dihydroxy(imidoarylene) monomer 1. The syntheses of poly(arylene ether)s were carried out in DMAc in the presence of anhydrous K2CO3 by a nucleophilic substitution reaction between the bisphenol and activated difluoro compounds. Poly(arylene t...

A series of new high molecular weight poly(arylene ether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have been synthesized. The inherent viscosities of these polymers are in the range of 0.33–0.64 dL/g. They are amorphous and readily soluble in chloroform, DMF, and DMAc. The glass transition temperatures of the polymers range from...