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Recent Publications

1. Baig, N.; Shetty, S.; Al-Mousawi, S.; Al-Sagheer, F.; Alameddine, B.; “Synthesis, Characterization, Thermal, and Optical Properties of Conjugated Co-Polymers Derived from Phenanthrene-9,10-dione- and Dibenzo[f,h]quinoxaline” Mterials Today Chemistry 2018, Accepted.

Abstract: Donor-Acceptor (D-A) conjugated polymers bearing phenanthrene-9,10-dione and dibenzo[f,h]quinoxaline as the acceptor units were synthesized via an optimized Suzuki cross-coupling reaction. Each of the abovementioned acceptors was reacted with three different donor co-monomers, namely, fluorene, carbazole and silafluorene derivatives bearing long alkyl chains. The resulting co-polymers display excellent solubility in common organic solvents with high chemical stability, allowing for the determination of their structural, thermal, and optical properties by various analytical techniques.

 

2. Alameddine, B.; Baig, N.; Shetty, S.; Al-Mousawi, S.; Al-Sagheer, F.; “Triptycene-Containing Poly(vinylene sulfone) Derivatives From a Metal-Free Thiol-Yne Click Polymerization Followed by a Mild Oxidation Reaction” Polymer 2018, 154, 233-240. DOI: 10.1016/j.polymer.2018.09.020

 

 

Abstract: Triptycene-derived vinyl sulfide polymers 4a-d were synthesized from a versatile catalyst-free thiol-yne click reaction using 1,4-diethynyl triptycene 1 with various aryl dithiol building blocks 3a-d. The resulting triptycene-bearing poly(vinylene sulfide)s 4a-d display excellent solubility and chemical stability allowing for their structural, thermal, and photophysical characterization by various instrumental analysis techniques. The thioether groups in polymers 4a-d were selectively oxidized into their respective sulfone derivatives via mild reaction conditions affording the corresponding triptycene-based poly(vinylene sulfone)s 5a-d in quantitative yield.

 

3. Baig, N.; Shetty, S.; Al-Mousawi, S.; Al-Sagheer, F.; Alameddine, B. “Influence of Size and Nature of the Aryl Diborate Spacer on the Intrinsic Microporosity of Iron(II) Clathrochelate Polymers” Polymer 2018, 151, 164-170. DOI: 10.1016/j.polymer.2018.07.069

Abstract: New polyclathrochelate derivatives were obtained using the mild one-step polycondensation reaction of an iron(II) center chelated to three polar furil dioxime side groups and doubly capped with various aryl diborate central spacers. Nitrogen adsorption measurements of the polychlathrochelates (PCL1-4) reveal a strong correlation between the intrinsic microporosity and the nature of aryl diborate spacer whose small size (PCL1) or contorted structure (PCL2) afford polymers with Brunauer-Emmett-Teller (BET) surface areas of ~396 m2/g and ~275 m2/g, respectively. On the other hand, the BET surface area of the polymer diminishes either when the aryl diborate spacer has free rotation axes (PCL3) or a laterally extended aromatic structure (PCL4).

 

4. Alameddine, B.; Baig, N.; Shetty, S.; Al-Mousawi, S.; Al-Sagheer, F., “Tuning the optical properties of ethynylene triptycene-based copolymers via oxidation of their alkyne groups into α-diketones” Journal of Polymer Science Part A: Polymer Chemistry 2018, 56, 931-937.

DOI: 10.1002/pola.28971

 

 

Abstract: The synthesis of ethynylene triptycene-based copolymers with various aromatic spacers (3a-d) is reported using the palladium-catalyzed Sonogashira cross-coupling reaction. The alkyne groups of 3a-d were oxidized into their respective α-diketone copolymers 4a-d. Formation of 3,4a-d was confirmed by several characterization techniques, such as, gel permeation chromatography (GPC), 1H- and 13C-nuclear magnetic resonance (NMR), FT-infrared (FTIR), UV-vis absorption, and emission spectroscopies. It was found that the nature of the aromatic spacer influences the emission properties of the target α-diketone triptycene copolymers, causing either a red or blue-shift with respect to that of their ethynylene triptycene copolymer synthons. Copolymers 4a-c with fluorene spacers reveal emission in the range of 440-475 nm, thus, qualifying them to act as blue emitters.

 

5. Alameddine, B.; Baig, N.; Shetty, S.; Al-Sagheer, F.; Al-Mousawi, S., “Microwave-Assisted [4+2] Diels-Alder Cycloaddition of 1,4-Diethynyl Triptycene with Various Cyclopentadienone Derivatives: Promising Building Blocks for Polymer Networks” Asian Journal of Organic Chemistry 2018, 7, 378-382. DOI: 10.1002/ajoc.201700655

 

 

 

Abstract: New triptycene derivatives substituted at their 1,4- positions with tetraphenylbenzene and diphenyltriphenylene moieties were prepared by microwave-assisted [4+2] Diels-Alder cycloaddition reaction in very good yields. The target compounds were characterized by 1H- and 13C- nuclear magnetic resonance (NMR), high resolution mass spectrometry (HR-MS), UV-Visible and emission spectrophotometry. In addition, single crystal X-ray diffraction for two of these derivatives are presented. The tetra- and octa- brominated triptycene compounds underwent palladium-catalyzed Suzuki-Miyaura cross-coupling reactions affording the desired products in very good yields. This successful tetra- and octa- fold substitution paves the way for the employment of these new synthons to prepare polymer networks for various applications.

 

6. Alameddine, B.; Shetty, S.; Anju, R. S.; Al-Sagheer, F.; Al-Mousawi, S. Highly soluble metal-organic polymers based on iron(II) clathrochelates and their gelation induced by sonication. European Polymer Journal 2017, 95, 566-574. DOI: 10.1016/j.eurpolymj.2017.08.049

 

 

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.

 

 

7. Alameddine, B.; Sobhana Anju, R.; Shetty, S.; Baig, N.; Al-Mousawi, S.; Al-Sagheer, F. Direct synthesis of polyaromatic chains of tribenzopentaphene copolymers through cyclodehydrogenation of their poly-tetraphenylbenzene precursors. Journal of Polymer Science Part A: Polymer Chemistry 2017, 55, 3565-3572. DOI: 10.1002/pola.28739

 

 

Abstract: Three polyaromatic-based polymers are reported to contain co-monomers of trapezoidal tribenzopentaphene (TBP) polycyclic aromatic hydrocarbons. The synthetic strategy consists of initially making highly soluble tetraphenylbenzene copolymers 4a–c, followed by a cyclodehydrogenation/aromatization reaction to obtain target polymers 5a–c. The polymers were characterized by gel permeation chromatography, FT-IR, UV-vis, emission, 1H-, and 13C-nuclear magnetic resonance spectroscopy. The target polymers 5a–c reveal emission spectra in the range of 430–480 nm; thus, qualifying them to act as blue emitters. Investigation of the polymers optical properties and their correlation with density functional theory calculations suggest a distorted TBP core from planarity caused by the introduction of a dodecyl group at its wide edge.

 

8. Alameddine, B.; Shetty, S.; Baig, N.; Al-Mousawi, S.; Al-Sagheer, F. Synthesis and characterization of metalorganic polymers of intrinsic microporosity based on Iron(II) clathrochelate. Polymer 2017, 122, 200-207. DOI:10.1016/j.polymer.2017.1006.1048

 

 

Abstract: Four Iron(II) clathrochelate derived polymers (P1-4) were synthesized under mild reaction conditions using iron(II) chloride with benzene-1,4-diboronic acid in presence of various vicinal dioxime moieties. The polymers were characterized by different instrumental analyses techniques and their structures were further confirmed by comparison of their respective synthesized prototypical monomers (M). Evaluation of P1-4 intrinsic microporosity was carried out by nitrogen adsorption measurements where polymer P4 reveals a Brunauer-Emmett-Teller (BET) surface area of 412 m2/g and average pore volume of 0.36 cm3/g.

 

9. Alameddine, B.; Anju, R. S.; Shetty, S; Al-Sagheer, F.; Jenny, T. A.; Mousawi, S., “Laterally Stretched Polycyclic Aromatic Hydrocarbons: Synthesis of Dibenzophenanthroheptaphene and Tetrabenzotriphenyleno-pyranthrene Derivatives”, New J. Chem., 2017, 41, 6025-6032. DOI: 10.1039/C7NJ00371D

 

 

Abstract: Efficient methods for the synthesis of dibenzophenanthroheptaphene (DBPH) and tetrabenzotriphenylenopyranthrene (TBTP) were developed. As a result, a series of unprecedented derivatives of DBPH (1a–c) and TBTP (2a–b) were conventionally obtained from the Scholl cyclodehydrogenation reaction of their respective tribenzopentaphene synthons. An alternative convergent synthesis of DBPH is also shown herein. The novel compounds were fully characterized by high-resolution matrix-assisted laser desorption ionization time of flight mass spectrometry (HR-MALDI-TOF-MS), nuclear magnetic resonance (NMR), UV-Vis absorption and emission spectroscopy. In addition, density functional calculations were carried out to gain insight into the structure and electronic properties of these novel molecules, which corroborates the experimental observations.

 

10. Alameddine, B.; Anju, R.S., Al-Sagheer, F., Jenny, T. “Tribenzopentaphene Derivatives with Lateral Aromatic Groups: Effect of Substituents’ Nature and Position on Conjugation”, New J. Chem., 2016, 40, 10363-10370. DOI: 10.1039/C1036NJ02563C

 

  • Nine new derivatives of the trapezoidal tribenzopentaphene (TBP) polycyclic aromatic hydrocarbon (PAH) were synthesized via the Suzuki–Miyaura palladium catalyzed cross-coupling reaction. The novel TBP derivatives, which bear various rigid and flexible aromatic groups either at their more accessible (R1) or congested (R2) bases, were fully characterized using high resolution mass spectrometry (HR-MS), nuclear magnetic resonance (NMR), UV-Vis absorption and emission spectroscopy. Our investigation reveals that extended conjugation between TBP and the aromatic side groups is possible when the latter are carefully selected and attached at the TBP wide base (R1), which causes an emission red-shift of the resulting target compounds. On the other hand, emission properties and density functional calculations suggest that attaching side groups at the sterically demanding base position (R2) induces a pronounced distortion from the planarity of the TBP central core structure.

 

11. G. Cecot, B. Alameddine, S. Geremia, R. Scopelliti, F. T. Farzaneh, E. Solari and K. Severin, “Large heterometallic coordination cages with gyrobifastigium-like geometry”, Chem. Commun., 2016, , 11243-11246.  10.1039/c6cc06066h

 

Abstract: Large (Mw > 10 kDa) heterometallic coordination cages with gyrobifastigium-like geometry are obtained by using metalloligands with sterically demanding FeII clathrochelate cores and four divergent pyridyl groups. Upon reaction with cis-blocked PtII and PdII complexes, MII8L4 cages are formed. The gyrobifastigium geometry of these cages is in contrast to the barrel-like structures which are typically observed for metallasupramolecular assemblies with M8L4 stoichiometry.

 

12. Alameddine, B.; Rice, A.; Jenny, T. A.; Luscombe, C. “Synthesis of Arylamine Tribenzopentaphenes and Investigation of their Hole Mobility”, ChemistryOpen 2015, 4, 453. DOI: 10.1002/open.201500064

 

 

Abstract: We report the versatile synthesis of two tribenzo[fj,ij,rst]pentaphene (TBP) derivatives bearing two diarylamine substituents attached at the opposite ends of the aromatic core. Field effect transistor (FET) devices of the bis-diarylamine-TBP compounds were fabricated using spin coating under different concentrations, spin speed, and solvent conditions. Emission spectra and surface investigation by atomic force microscopy (AFM) reveal the formation of aggregates induced by the strong π–π stacking of the aromatic core leading to island features, and thus, unexpected low hole mobilities. The synthetic strategy we show herein, however, offers the possibility to decorate the TBP core structure with various charge-carrier peripheral groups and optimized alkyl chains, which should improve the crystalline property of their thin films upon deposition, leading consequently to a better hole transport mobility.

 

13. Alameddine, B.; Aebischer, O.; Heinrich, B; Donnio, B.; Guillon, D.; Jenny T. A. “Influence of Linear and Branched Perfluoroalkylated Side Chains on the π-π Stacking Behavior of Hexa-peri-hexabenzocoronene and Thermochemical Properties”, Supramol. Chem.

 

Abstract: The thermotropic properties and self-assembly of two different series of hexa-peri-hexabenzocoronenes (HBC) bearing either linear or branched perfluoroalkylated side chains, each with a wide range of alkyl spacer and perfluorinated tail lengths, have been studied. Correlations between thermogravimetric analysis, differential scanning calorimetry, polarised optical microscopy and small-angle X-ray scattering experiments revealed, as expected, that the transition temperatures and phase stability are influenced by the determining roles of the aliphatic spacer length and odd/even nature, as well as the size and structure (linear vs. bifurcation) of the perfluorinated sections. Most of the investigated HBC derivatives showed a single-column hexagonal columnar phase, where the columns are structured by a double segregation process between HBC aromatic cores and aliphatic spacers, on the one hand, and between aliphatic spacers and fluorinated tails, on the other hand. For the derivatives with long linear spacers, cores of untilted or quasi-untilted HBC stacks are surrounded by a cylindrical aliphatic envelope segregated from the fluorinated periphery, whereas for those with shorter linear spacers, the same structure is kept, except that the aliphatic envelope deviates from cylindricality and causes a symmetry break to rectangular envelope for the first term of the series. Of the four HBC with branched spacers, two are amorphous, whereas a columnar phase is maintained for the other two derivatives, but with tilted HBC stacks. Consequently, the evolution of the polymorphism in the series could be correlated with the variation of both interface areas.

 

 

14. Antony, J.; Alameddine, B.; Jenny, T. A.; Grimme, S. “Theoretical Study of the Stacking Behavior of Selected Polycondensed Aromatic Hydrocarbons with Various Symmetries”, J. Phys. Chem. A, 2013, 117, 616-625. DOI: 10.1021/jp3075207

 

 

Abstract: 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.

 

15. Alameddine, B; Schindler, M.; Jenny, T. A.; “Synthesis of Alkyl- Substituted Tribenzopentaphenes as Versatile Polycondensed Aromatic Hydrocarbon π-π Stacking Building Blocks” Synthesis, 2012, 44, 1928-1934. DOI: 10.1055/s-0031-1291010

 

16. Aebischer, O.; Alameddine, B.; Jenny, T. A.; “Hexabenzocoronenes - Controlling their Self-assembly by Engineering the Lateral Substituents” Chimia, 2008, 62, 967.DOI: 10.2533/chimia.2008.967

 

17. Aebischer, A.; Aebischer, O. F.; Alameddine, B.; B. Donnio; Dadras, M.; Güdel, H.-U.; Guillon, D.; Jenny, T. A. “Controlling the Lateral Aggregation of Perfluoroalkylated Hexabenzocoronenes” J. Mat. Chem. 2007, 17(13), 1262-1267. DOI: 10.1039/b616057c

 

18. Alameddine, B.; Aebischer, O.; Savary, C.; Jenny, T. A.; “Synthesis of Perfluoroalkylated Bulky Triaryl Amines” Synthesis, 2007, 2, 271-276.DOI: 10.1055/s-2006-958953

 

19. Sanaur, S.; Whalley, A.; Alameddine, B.; Carnes, M.; Nuckolls, C.;“ Jet-printed Electrodes and Semiconducting Oligomers for Elaboration of Organic Thin-film Transistors” Organic Electronics, 2006, 7, 423-427. DOI: 10.1016/j.orgel.2006.05.003

 

20. Aebischer, O.; Aebischer, N.; Tondo, P.; Alameddine, B.; Dadras, M.; Guedel, H.; Jenny T. A.“Self-aggregated Perfluoroalkylated Hexa-peri-hexabenzocoronenes Fibers Observed in Cryo-SEM and Fluorescence Spectroscopy” Chemical Communications, 2006, 40, 4221-4223.

DOI: 10.1039/b609056g

 

21. Aebischer, O.; Tondo, P.; Alameddine, B.; Jenny T. A.“Synthesis of Novel Perfluorinated Hexa-peri-hexabenzocoronenes” 2006, Synthesis, 17, 2891-2896.DOI: 10.1055/s-2006-942550

 

22. Alameddine, B.; Aebischer, O.; Amrein, W.; Deschenaux, R.; Donnio, B.; Guillon, D.; Savary, C.; Scanu, D.; Scheidegger, O.; Jenny T. A. “ Mesomorphic Hexabenzo- coronenes Bearing Perfluorinated Chains” Chem. Mater.; 2005, 17(19), 4798 – 4807.DOI: 10.1021/cm050612o

 

23. Tran, F.; Alameddine, B.; Jenny, T. A.; Wesolowski, T. “π-Stacking Behavior of Selected Nitrogen-Containing PAHs” J. of Phys. Chem. A 2004, 108(42), 9155-9160.DOI: 10.1021/jp048713h