869 research outputs found
BsubAc: Precursor and Macrocycle Synthesis of Boron Subanthracocyanine
No full textThe synthesis of the anthracocyanine precursor, 9,10-diphenyl-2,3-dicynanoanthracene (Ph2DCAnt), was successfully made with a yield of 18%. This was done using two Diels-Alder reactions followed by a double dehydration step. Multiple attempts were made to create this precursor and modifications from Rainbolt & Miller method allowed for a precursor with low yield but better purity than previous attempts. The boron subanthracocyanine macrocycle was made with boron trichloride in p-xylene and the optimized precursor (Ph2DCAnt), using 1,2-dichlorobenzene as a solvent. This compound was confirmed to be made via UV-Vis characterization.M.Sc
HCNO AS A SEMIRIGID BENDER: THE DEGENERATE STATE
No full textAuthor Institution: Physikalisch-Chemisches Institut, Justus-Liebig-Universitaet Giessen; Herzberg Institute of Astrophysics, National Research Council of CanadaThe manifold of large amplitude states (due to the HCN bending vibration at ) superimposed on the CNO bending state at for fulminic acid HCNO has been analyzed using a modified version of the semirigid bender model previously described by Bunker et The bending mode is degenerate in the linear limit and the semirigid bender Hamiltonian has been modified to account for the vibrational angular momentum around the molecular axis in the the linear limit, and for -doubling effects. Some of the experimental data used in this analysis were obtained from a spectrum of HCNO between 500 and recorded on the high-resolution infrared Bomem interferometer at the Herzberg Institute of Astrophysics, Ottawa. From this spectrum, molecular constants have been determined for a number of vibrational states not previously observed: and . P.R. Bunker, B.M. Landsberg and B.P. winnewisser, J. Mol, spectrosc. 74, 9 (1979
Accessing New Synthetic Pathways for Asymmetric Boron Subphthalocyanines and Considering a More Sustainable Boron Source
No full textWhile the selective synthesis of semi-symmetric ABAB- or AABB-type phthalocyanines has been published, no known synthetic pathway has been developed for asymmetric AAB-type boron subphthalocyanines (BsubPcs). A set of templated BsubPc approaches was investigated by pre-arranging the macrocyclic sub-units and ultimately forming the macrocycle through addition of a boron trihalide reagent. The methods employed however were unable to yield any result of interest. Separately, the syntheses of boron subnaphthalocyanines (BsubNcs) occurring between dicyanonaphthalene and a boron trihalide to form the macrocycle of interest are known to also introduce random bay-position halogenation. In addition, the standard usage of boron trihalides as the boron source presents recurring issues relating to the low boiling points, toxicity and reactivitiy to air and moisture they possess. The usage of triphenyl borates as alternative boron sources was considered, being a more sustainable boron source. A synthetic pathway using triphenyl borates to BsubPcs and BsubNc was developed.M.Sc.2023-06-29 00:00:0
Applications of Piers-Rubinsztajn Chemistry: Synthesis of Materials for Organic Electronics
No full textSince the advent of the age of organic electronics, new materials are being developed regularly for use in these types of devices. Their processing methods have also evolved over the years, resulting in new, commercially-available applications. The application of these materials from solution, also known as solution processing, is lower-cost and less energy intensive with many other added benefits. To that end, this thesis explores the Piers-Rubinsztajn reaction as a tool to enable the solution processing of organic electronic materials.
Piers-Rubinsztajn chemistry is a versatile, expedient reaction using an organic Lewis acidic catalyst tris(pentafluorophenyl)borane to couple a Si-H bond with an oxygen based nucleophile. This type of chemistry is underexplored in the field of materiasl development for organic electronics applications. This chemistry can be used to incorporate different types of siloxane oligomers into the structure of an organic electronic material, thus merging the properties of siloxane materials, such as flexibility, with those of the original compound. This methodology is used in this thesis to alter the physical properties of a variety of organic electronic materials to enable and ameliorate their solution processing.
Chapters 2 to 5 explore the use of Piers-Rubinsztajn chemistry to cross-link triarylamine derivatives, to allow sequential solution processing for its application in an organic light emitting diode. Chapter 6 involves the synthesis of phenoxylated siloxane polymers, via Piers-Rubinsztajn chemistry, as a new material with improved organic-phase miscibility, for potential application in an organic electronic device. Chapters 7 and 8 follow the scale-up synthesis and application of a liquid triarylamine derivative in a dye-sensitized solar cell. Finally, Chapter 9 will cover the use of Piers-Rubinsztajn chemistry to functionalize insoluble silicon phthalocyanine derivatives to enable their use in bulk-heterojunction organic photovoltaics.Ph.D.2020-01-09 00:00:0
Boron Subnaphthalocyanines: The First Unsubstituted Examples, New Boron Lewis Acids, Random Bay Position Halogenation, and Computational Material Screening
No full textBoron subnaphthalocyanines (BsubNcs) are a class of materials that our lab has shown to be alloyed mixtures of derivatives that are randomly chlorinated in the bay positions, resulting from their formation from boron trichloride. These alloyed mixtures were shown to have a positive influence on the functionality of organic photovoltaics whereby an increase in the amount of bay position chlorination was found to increase power conversion efficiency. The bay position chlorinated BsubNcs were also found to be stable in the ambient environment within organic solar cells which also justified their further development. The alloying of these materials leads to a potentially unique opportunity to tailor the alloyed mixture for a desired application by blending pure or partially separated samples of BsubNcs. Herein we lay the groundwork for achieving this goal. We explore the separation of bay position halogenated (chlorinated and brominated) BsubNcs enabled by their functionalization with phenolic axial moieties. We develop an understanding of the dependence of their physical properties on the frequency of bay position halogenation and developed improved analytical techniques for this class of materials. We also present a new method for the synthesis of BsubNcs that circumvents the generation of bay position halogenated species, resulting in the first examples of pure unsubstituted BsubNcs. To achieve this, we proposed that a non-halide boron based Lewis acid is required, and that a balance of the Lewis acidity of the boron source and the Lewis basicity of the BsubNc precursor can guide the synthesis of BsubNcs. After achieving this desired outcome, we also explored the application of this method for the synthesis of the related boron subphthalocyanines (BsubPcs) and as the macrocycles were formed, we found potential for the broad application of this methodology. A computationally calibrated model to screen key material properties of BsubPcs for their accelerated development was also developed. We uniquely found a method that can achieve this with a standard laptop and software that is free to academia. We anticipate that incorporation of BsubNcs into the model will be possible as the key material properties have been determined for BsubNcs developed in this thesis.Ph.D.2022-11-29 00:00:0
OPTIMIZATION AND NOVEL SYNTHESIS OF CHLORINATED BORON SUBNAPHTHALOCYANINES FOR USE IN ORGANIC PHOTOVOLTAICS
No full textBoron Subnaphthalocyanines (BsubNC) make up a small class of isoindoles in the field of organic electronics. The material is often difficult to isolate, produce at scale, and reliably reproduce. Despite the challenges associated with the larger isoindoles, they have demonstrated strong performance in fullerene free devices.
The work herein looked to investigate the synthesis of a new starting material for synthesis of BsubNCs. The synthesis of 1,4-dichloro-2,3-dicyanonaphthalene (1,4-Cl-2,3-DCN) as a precursor for the controlled formation of Cl-Cl6-BsubNc macrocycles.
A study is made into the optimization of boron subnaphthalocyanines (BsubNcs) synthesis using microwave reactors, a promising method to enhance energy efficiency and reduce reaction times. Traditional synthesis of BsubNcs
Additionally, The synthesis and yet to be isolated Cl-Cl6-BSubNC in hopes of addressing the challenge of random halogenation that has been endemic to their synthesis while unlocking a new molecule in the Boron macrocycle toolbox.M.Sc
Applications of Piers-Rubinsztajn Chemistry: Synthesis of Materials for Organic Electronics
No full textSince the advent of the age of organic electronics, new materials are being developed regularly for use in these types of devices. Their processing methods have also evolved over the years, resulting in new, commercially-available applications. The application of these materials from solution, also known as solution processing, is lower-cost and less energy intensive with many other added benefits. To that end, this thesis explores the Piers-Rubinsztajn reaction as a tool to enable the solution processing of organic electronic materials.
Piers-Rubinsztajn chemistry is a versatile, expedient reaction using an organic Lewis acidic catalyst tris(pentafluorophenyl)borane to couple a Si-H bond with an oxygen based nucleophile. This type of chemistry is underexplored in the field of materiasl development for organic electronics applications. This chemistry can be used to incorporate different types of siloxane oligomers into the structure of an organic electronic material, thus merging the properties of siloxane materials, such as flexibility, with those of the original compound. This methodology is used in this thesis to alter the physical properties of a variety of organic electronic materials to enable and ameliorate their solution processing.
Chapters 2 to 5 explore the use of Piers-Rubinsztajn chemistry to cross-link triarylamine derivatives, to allow sequential solution processing for its application in an organic light emitting diode. Chapter 6 involves the synthesis of phenoxylated siloxane polymers, via Piers-Rubinsztajn chemistry, as a new material with improved organic-phase miscibility, for potential application in an organic electronic device. Chapters 7 and 8 follow the scale-up synthesis and application of a liquid triarylamine derivative in a dye-sensitized solar cell. Finally, Chapter 9 will cover the use of Piers-Rubinsztajn chemistry to functionalize insoluble silicon phthalocyanine derivatives to enable their use in bulk-heterojunction organic photovoltaics.Ph.D.2020-01-09 00:00:0
Culture on the Brink : Ideologies of Technology
No full text"Examining the shifting roles of technology in diverse public and private spheres, such as work, leisure, art, and war, the texts included here were presented by the participants of a three-day conference held at Diain Spring 1992." -- p. 1
Hybrid and Biosourced Platforms for The Design of Complex Isoindole-Based Macrocycles as Advanced Organic Electronic Materials
No full textOrganic (opto)electronics, including organic photovoltaics (OPVs) and organic light-emitting diodes (OLEDs), are rapidly advancing, and consequently driving up demand for the materials used in these devices. The porphyrinoid family stands out as promising candidates for use in organic electronics, serving as the building blocks of photosynthetic systems and a nature-inspired platform for organic semiconductors. Porphyrinoids, macrocycles composed of isoindole units, offer several advantageous characteristics including exceptional light absorption, versatile chemistry, highly tunable properties via chemical modifications, high ambient stability, and scalable material preparation. This thesis explores the development of new π-extended, red-absorbing isoindole-based macrocycles with small bandgap energies (<< 2.0 eV) and varying molecular symmetries (Cs, C3v, D4h), hybrid topologies, or biosourced compositions as organic electronic materials. Specifically, three classes of compounds are investigated including boron subphthalocyanine–subnaphthalocyanine hybrids (Bsub(Pc3-p-Ncp)s), nitrogen-substituted boron subnaphthalocyanines (BsubNcs), and biosourced silicon phthalocyanines (SiPcs). The procurement of these materials centers on ortho-dinitrile precursors with site-specific substitutions in the α/α’ positions. It was revealed that perfluorinated F8Bsub(Pc2-Nc1) hybrids (p = 1) exhibit uniquely broad absorption spectra and narrow near-red emission compared to F8BsubPc hybrids, along with electrochemical versatility. A selective synthesis method for Bsub(Pc2-Nc1) hybrids was introduced, achieving high yields and precise control over structural and optical properties through sterically-driven mixed cyclotrimerization. The impact of π–π interactions on the solid-state arrangements of perfluorinated BsubPc-type hybrids was also examined, showing how arene-perfluoroarene interactions can be harnessed to direct the crystal packing of these macrocycles into rich molecular networks. Preliminary efforts into accessing nitrogen-substituted BsubNcs and their precursor materials emphasized computational modeling for energy level tuning and synthetic challenges during sustainable process development. Green chemistry approaches were leveraged to address the material sustainability of SiPcs by using biomass-derived precursors. This led to new α-methylated SiPc derivatives with a biorenewable carbon framework, enhanced red absorption, solubility, and electronic properties while demonstrating high atom and carbon economies. Together, these findings contribute to the expansion of available porphyrinoids as candidate organic semiconductors and understanding of their structure-property relationships. By developing porphyrinoid materials with tailored properties and sustainable synthetic methods, this work offers promising solutions for organic electronic applications.Ph.D.2025-11-12 00:00:0
SIMULATED ELECTRONIC SPECTRA OF HCN AND CNH OBTAINED WITH THE SEMIRIGID BENDER MODEL
No full textAuthor Institution: Herzberg Institute of Astrophysics, National Research Council Ottawa. Ontario; Department of Physics, Carleton University Ottawa, OntarioThe Semirigid Bender (SRB) model has been used to study the complete internal rotation of HCN into CNH for both the ground and first excited electronic states. The bending potential functions of these two states were obtained by fitting the SRB model to experimentally observed vibrationa1 energies and by incorporating various ab initio results where experimental data was lacking. The SRB wavefunctions obtained from these potential functions, combined with wave functions for the stretching vibrations, were then used to simulate the electronic spectra for both HCN and CNH
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