Bassam Alameddine - Academia.edu (original) (raw)

Papers by Bassam Alameddine

Journal of Applied Polymer Science

Polymers

The development of a simple and efficient synthetic methodology to engineer functional polymer ma... more The development of a simple and efficient synthetic methodology to engineer functional polymer materials for gas adsorption is necessary due to its relevance for various applications. Herein, we report the synthesis of metalorganic poly(vinylene sulfide) copolymers CTP1-3 with iron(II) clathrochelate of various side groups connected by tetraphenylbenzene units. CTP1-3 were subsequently oxidized into their respective poly(vinylene sulfone) copolymers CTP4-6 under green reaction conditions. The target copolymers CTP1-6 were characterized using various instrumental analysis techniques. Examination of the iodine adsorption properties of the copolymers revealed high iodine uptake properties, reaching 2360 mg g−1 for CTP2, and whose reusability tests proved its efficient regeneration, thus proving the importance of iron(II) clathrochelate polymers in iodine capture.

Polymers

We report the synthesis of three highly soluble metalorganic copolymers, TCP1–3, that were made f... more We report the synthesis of three highly soluble metalorganic copolymers, TCP1–3, that were made from a one-pot complexation of iron(II) clathrochelate units that are interconnected by various thioether-containing contorted groups. TCP1–3 were converted into their poly(vinyl sulfone) derivatives OTCP1–3 quantitatively via the selective oxidation of the thioether moieties into their respective sulfones. All of the copolymers, TCP1–3 and OTCP1–3, underwent structural analysis by various techniques; namely, 1H- and 13C-nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and gel permeation chromatography (GPC). The copolymers were tested as potent lithium ions adsorbents revealing a maximum adsorption (qm) value of 2.31 mg g−1 for OTCP2. Furthermore, this same copolymer was found to be a promising adsorbent of methylene blue (MEB); an isothermal adsorption study divulged that OTCP2’s uptake of MEB from an aqueous solution (followin...

RSC Advances, 2021

Copolymers TCP1–3 with Trӧger's base units and aryl thioether groups were made via a click re... more Copolymers TCP1–3 with Trӧger's base units and aryl thioether groups were made via a click reaction. Selective oxidation of the thioethers into sulfone groups afforded TCP4–6 which display up to 100% removal efficiency of methylene blue from water.

Polymer, 2021

Copolymer networks containing Tröger's base units TBP1-3 were synthesized in very good yields fro... more Copolymer networks containing Tröger's base units TBP1-3 were synthesized in very good yields from a Sonogashira cross-coupling reaction of a specially designed diethynyl Tröger's base synthon TB with various tetrabrominated aryl derivatives. Thermogravimetric analysis (TGA) of TBP1-3 discloses high 10% weight loss temperature values reaching up to 443 • C. Nitrogen adsorption measurements of the target copolymers TBP1-3 reveal a strong correlation between porosity and the geometry of the aryl spacer whose inflexible rigid structure (biphenyl, TBP1), contorted configuration (spirobifluorene, TBP2), or fused aromatic structure (pyrene, TBP3) affords Brunauer-Emmett-Teller (BET) surface areas ranging from ~586 m 2 g − 1 to ~620 m 2 g − 1. Inspection of the iodine adsorption properties of TBP1-3 reveals their significant uptake of iodine vapors reaching a maximum of 440 wt% for TBP1 whereas TBP2 exhibits a very good removal efficiency of iodine solution in hexane attaining 77% (q e = 192 mg g − 1). Furthermore, reusability tests disclose the possibility to regenerate the polymers even after several iodine adsorptions-desorption cycles.

RSC Advances, 2021

We report the synthesis of metalorganic copolymers made from the palladium catalyzed Sonogashira ... more We report the synthesis of metalorganic copolymers made from the palladium catalyzed Sonogashira cross-coupling reaction between various iron(ii) clathrochelate building blocks with diethynyl–triptycene and fluorene derivatives.

ChemistryOpen, 2021

Abstract We report the synthesis, characterization, and photophysical properties of novel metal o... more Abstract We report the synthesis, characterization, and photophysical properties of novel metal oxide nanoparticles (NPs) coated with specially designed fluorescein substituents which are capped with electron‐withdrawing groups. The fluorescein‐coated nanoparticles were synthesized in excellent yields, and their structures were confirmed using various advanced spectroscopic, instrumental, and surface analysis techniques, revealing the formation of the target functionalized nanoparticles (FNPs) which show superior chemical and thermal stabilities. In addition, the photophysical properties of the FNPs were examined using UV‐visible absorption and fluorescence spectroscopy. These latter techniques disclosed aggregation‐induced emission (AIE) properties for most of the target FNPs, namely those which are soluble in common organic solvents at selective concentration ranges of water fractions in the solvent mixture.

New Journal of Chemistry, 2020

Excellent yields, high stability and solubility. Mw = 36.5–152.0 kDa and Đ = 2.5–3.0. Deep-blue e... more Excellent yields, high stability and solubility. Mw = 36.5–152.0 kDa and Đ = 2.5–3.0. Deep-blue emission with quantum yields up to 17%.

Polymer Chemistry, 2020

A new class of conjugated polymers is prepared by means of a versatile palladium-catalyzed cyclop... more A new class of conjugated polymers is prepared by means of a versatile palladium-catalyzed cyclopentannulation reaction using a series of specially designed diethynyl aryl synthons with the commercially available 9,10-dibromoanthracene DBA monomer.

Microporous and Mesoporous Materials, 2020

This is a PDF file of an article that has undergone enhancements after acceptance, such as the ad... more This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

New J. Chem., 2017

The synthesis of new extended trapezoidal PAHs is shown. Tetra-alkylation of the most stretched d... more The synthesis of new extended trapezoidal PAHs is shown. Tetra-alkylation of the most stretched derivative induces a contorted structure.

New J. Chem., 2016

Functionalization of tribenzopentaphene with aromatic side groups distorts its core from planarit... more Functionalization of tribenzopentaphene with aromatic side groups distorts its core from planarity resulting in red-shifted emission.

European Polymer Journal, 2017

Abstract A series of clathrochelate polymers are reported by reacting iron(II) chloride with 9,9-... more Abstract A series of clathrochelate polymers are reported by reacting iron(II) chloride with 9,9-dialkyl fluorene-2,7-diboronic acid and various vicinal dioxime units. The novel polymers were fully characterized by 1H and 13C nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and UV–Vis absorption spectroscopy. The linearly-linked 2D organometallic polymers form oragnogel from 10 wt% concentrations in organic solvents of low and medium polarity.

The Journal of Physical Chemistry A, 2013

Stacked dimers of four polycondensed aromatic hydrocarbons, with structures varying from high to ... more Stacked dimers of four polycondensed aromatic hydrocarbons, with structures varying from high to reduced symmetries, have been calculated with dispersion-corrected density functional theory. The configurations of the stacked dimers are readily classified by two in-plane displacements and a relative rotation. The potential energy surface in these three coordinates was calculated with rigid monomers and appears to be slightly flat. Full geometry optimization was performed for selected low-energy structures, resulting in an energy ranking of a series of conformations whose geometries were characterized in considerable detail. The dissociation energy values reveal a clear preference for the symmetrical disk-shaped and triangular structures to dimerize into two in-plane-displaced arrangements, whereas the less symmetrical trapezoidal structures show a tendency to stack in displaced antiparallel over parallel arrangements. According to methodical checks, the key computational results, namely, the shape of the potential energy surface and the geometrical structures and energy ranking of dimer conformations, are essentially insensitive to computational assumptions such as the atomic orbital basis set and density functional chosen. This is shown in particular for the basis set superposition error, which, for the selected level of theory [B97-D3(BJ)/ TZV(d,p)] was estimated by the counterpoise correction procedure to be in the narrow range between 7% and 8% of the uncorrected dissociation energies.

Synthesis, 2006

The synthesis of several perfluoroalkylated hexabenzocoronene derivatives is described. The subst... more The synthesis of several perfluoroalkylated hexabenzocoronene derivatives is described. The substituents range from linear semiperfluoroalkylated chains to branched perfluoroalkylated chains. Novel strategies were applied to overcome the low solubility and the low reactivity of such chains.

Supramolecular Chemistry, 2013

Chemistry of Materials, 2005

Synthesis and characterization of new hexabenzocoronene (HBC) derivatives bearing perfluoroalkyla... more Synthesis and characterization of new hexabenzocoronene (HBC) derivatives bearing perfluoroalkylated chains are described. These disc-shaped polycondensed aromatic hydrocarbons are known to self-assemble by π-stacking into columnar architectures. The peripheral decoration with perfluorinated chains, well-known for their low van der Waals forces, leads as expected to reduced intercolumnar interactions. Powder X-ray diffraction and differential scanning calorimetry of these perfluoroalkylated HBCs proved liquid crystalline (LC) properties whose transition temperatures, mesophase stability, and nature depend on the detailed structure of these side chains, i.e., the ratio between aliphatic and perfluorinated parts. On the other hand, the insertion of a phenyl spacer between the aromatic core and the lateral chains increases the LC transition temperature and, surprisingly, switches the mesophase structure from columnar to smectic.

Chemical Communications, 2006

Journal of Applied Polymer Science

Polymers

The development of a simple and efficient synthetic methodology to engineer functional polymer ma... more The development of a simple and efficient synthetic methodology to engineer functional polymer materials for gas adsorption is necessary due to its relevance for various applications. Herein, we report the synthesis of metalorganic poly(vinylene sulfide) copolymers CTP1-3 with iron(II) clathrochelate of various side groups connected by tetraphenylbenzene units. CTP1-3 were subsequently oxidized into their respective poly(vinylene sulfone) copolymers CTP4-6 under green reaction conditions. The target copolymers CTP1-6 were characterized using various instrumental analysis techniques. Examination of the iodine adsorption properties of the copolymers revealed high iodine uptake properties, reaching 2360 mg g−1 for CTP2, and whose reusability tests proved its efficient regeneration, thus proving the importance of iron(II) clathrochelate polymers in iodine capture.

Polymers

We report the synthesis of three highly soluble metalorganic copolymers, TCP1–3, that were made f... more We report the synthesis of three highly soluble metalorganic copolymers, TCP1–3, that were made from a one-pot complexation of iron(II) clathrochelate units that are interconnected by various thioether-containing contorted groups. TCP1–3 were converted into their poly(vinyl sulfone) derivatives OTCP1–3 quantitatively via the selective oxidation of the thioether moieties into their respective sulfones. All of the copolymers, TCP1–3 and OTCP1–3, underwent structural analysis by various techniques; namely, 1H- and 13C-nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and gel permeation chromatography (GPC). The copolymers were tested as potent lithium ions adsorbents revealing a maximum adsorption (qm) value of 2.31 mg g−1 for OTCP2. Furthermore, this same copolymer was found to be a promising adsorbent of methylene blue (MEB); an isothermal adsorption study divulged that OTCP2’s uptake of MEB from an aqueous solution (followin...

RSC Advances, 2021

Copolymers TCP1–3 with Trӧger's base units and aryl thioether groups were made via a click re... more Copolymers TCP1–3 with Trӧger's base units and aryl thioether groups were made via a click reaction. Selective oxidation of the thioethers into sulfone groups afforded TCP4–6 which display up to 100% removal efficiency of methylene blue from water.

Polymer, 2021

Copolymer networks containing Tröger's base units TBP1-3 were synthesized in very good yields fro... more Copolymer networks containing Tröger's base units TBP1-3 were synthesized in very good yields from a Sonogashira cross-coupling reaction of a specially designed diethynyl Tröger's base synthon TB with various tetrabrominated aryl derivatives. Thermogravimetric analysis (TGA) of TBP1-3 discloses high 10% weight loss temperature values reaching up to 443 • C. Nitrogen adsorption measurements of the target copolymers TBP1-3 reveal a strong correlation between porosity and the geometry of the aryl spacer whose inflexible rigid structure (biphenyl, TBP1), contorted configuration (spirobifluorene, TBP2), or fused aromatic structure (pyrene, TBP3) affords Brunauer-Emmett-Teller (BET) surface areas ranging from ~586 m 2 g − 1 to ~620 m 2 g − 1. Inspection of the iodine adsorption properties of TBP1-3 reveals their significant uptake of iodine vapors reaching a maximum of 440 wt% for TBP1 whereas TBP2 exhibits a very good removal efficiency of iodine solution in hexane attaining 77% (q e = 192 mg g − 1). Furthermore, reusability tests disclose the possibility to regenerate the polymers even after several iodine adsorptions-desorption cycles.

RSC Advances, 2021

We report the synthesis of metalorganic copolymers made from the palladium catalyzed Sonogashira ... more We report the synthesis of metalorganic copolymers made from the palladium catalyzed Sonogashira cross-coupling reaction between various iron(ii) clathrochelate building blocks with diethynyl–triptycene and fluorene derivatives.

ChemistryOpen, 2021

Abstract We report the synthesis, characterization, and photophysical properties of novel metal o... more Abstract We report the synthesis, characterization, and photophysical properties of novel metal oxide nanoparticles (NPs) coated with specially designed fluorescein substituents which are capped with electron‐withdrawing groups. The fluorescein‐coated nanoparticles were synthesized in excellent yields, and their structures were confirmed using various advanced spectroscopic, instrumental, and surface analysis techniques, revealing the formation of the target functionalized nanoparticles (FNPs) which show superior chemical and thermal stabilities. In addition, the photophysical properties of the FNPs were examined using UV‐visible absorption and fluorescence spectroscopy. These latter techniques disclosed aggregation‐induced emission (AIE) properties for most of the target FNPs, namely those which are soluble in common organic solvents at selective concentration ranges of water fractions in the solvent mixture.

New Journal of Chemistry, 2020

Excellent yields, high stability and solubility. Mw = 36.5–152.0 kDa and Đ = 2.5–3.0. Deep-blue e... more Excellent yields, high stability and solubility. Mw = 36.5–152.0 kDa and Đ = 2.5–3.0. Deep-blue emission with quantum yields up to 17%.

Polymer Chemistry, 2020

A new class of conjugated polymers is prepared by means of a versatile palladium-catalyzed cyclop... more A new class of conjugated polymers is prepared by means of a versatile palladium-catalyzed cyclopentannulation reaction using a series of specially designed diethynyl aryl synthons with the commercially available 9,10-dibromoanthracene DBA monomer.

Microporous and Mesoporous Materials, 2020

This is a PDF file of an article that has undergone enhancements after acceptance, such as the ad... more This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

New J. Chem., 2017

The synthesis of new extended trapezoidal PAHs is shown. Tetra-alkylation of the most stretched d... more The synthesis of new extended trapezoidal PAHs is shown. Tetra-alkylation of the most stretched derivative induces a contorted structure.

New J. Chem., 2016

Functionalization of tribenzopentaphene with aromatic side groups distorts its core from planarit... more Functionalization of tribenzopentaphene with aromatic side groups distorts its core from planarity resulting in red-shifted emission.

European Polymer Journal, 2017

Abstract A series of clathrochelate polymers are reported by reacting iron(II) chloride with 9,9-... more Abstract A series of clathrochelate polymers are reported by reacting iron(II) chloride with 9,9-dialkyl fluorene-2,7-diboronic acid and various vicinal dioxime units. The novel polymers were fully characterized by 1H and 13C nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and UV–Vis absorption spectroscopy. The linearly-linked 2D organometallic polymers form oragnogel from 10 wt% concentrations in organic solvents of low and medium polarity.

The Journal of Physical Chemistry A, 2013

Stacked dimers of four polycondensed aromatic hydrocarbons, with structures varying from high to ... more Stacked dimers of four polycondensed aromatic hydrocarbons, with structures varying from high to reduced symmetries, have been calculated with dispersion-corrected density functional theory. The configurations of the stacked dimers are readily classified by two in-plane displacements and a relative rotation. The potential energy surface in these three coordinates was calculated with rigid monomers and appears to be slightly flat. Full geometry optimization was performed for selected low-energy structures, resulting in an energy ranking of a series of conformations whose geometries were characterized in considerable detail. The dissociation energy values reveal a clear preference for the symmetrical disk-shaped and triangular structures to dimerize into two in-plane-displaced arrangements, whereas the less symmetrical trapezoidal structures show a tendency to stack in displaced antiparallel over parallel arrangements. According to methodical checks, the key computational results, namely, the shape of the potential energy surface and the geometrical structures and energy ranking of dimer conformations, are essentially insensitive to computational assumptions such as the atomic orbital basis set and density functional chosen. This is shown in particular for the basis set superposition error, which, for the selected level of theory [B97-D3(BJ)/ TZV(d,p)] was estimated by the counterpoise correction procedure to be in the narrow range between 7% and 8% of the uncorrected dissociation energies.

Synthesis, 2006

The synthesis of several perfluoroalkylated hexabenzocoronene derivatives is described. The subst... more The synthesis of several perfluoroalkylated hexabenzocoronene derivatives is described. The substituents range from linear semiperfluoroalkylated chains to branched perfluoroalkylated chains. Novel strategies were applied to overcome the low solubility and the low reactivity of such chains.

Supramolecular Chemistry, 2013

Chemistry of Materials, 2005

Synthesis and characterization of new hexabenzocoronene (HBC) derivatives bearing perfluoroalkyla... more Synthesis and characterization of new hexabenzocoronene (HBC) derivatives bearing perfluoroalkylated chains are described. These disc-shaped polycondensed aromatic hydrocarbons are known to self-assemble by π-stacking into columnar architectures. The peripheral decoration with perfluorinated chains, well-known for their low van der Waals forces, leads as expected to reduced intercolumnar interactions. Powder X-ray diffraction and differential scanning calorimetry of these perfluoroalkylated HBCs proved liquid crystalline (LC) properties whose transition temperatures, mesophase stability, and nature depend on the detailed structure of these side chains, i.e., the ratio between aliphatic and perfluorinated parts. On the other hand, the insertion of a phenyl spacer between the aromatic core and the lateral chains increases the LC transition temperature and, surprisingly, switches the mesophase structure from columnar to smectic.

Chemical Communications, 2006