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Borinic acid polymers and their supramolecular networks
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Baraniak, Monika Katarzyna. Borinic acid polymers and their supramolecular networks. Retrieved from https://doi.org/doi:10.7282/t3-89kh-f793

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TitleBorinic acid polymers and their supramolecular networks
NameBaraniak, Monika Katarzyna (author); Jaekle, Frieder (chair); Galoppini, Elena (member); Huskey, Phillip (member); Iovine, Peter M (member); Rutgers University; Graduate School - Newark
Date Created2021
Other Date2021-10 (degree)
SubjectPolymer chemistry, Polymers, Catalysis, Borinic acids, Dynamic covalent bonding, Self-assembly, Supramolecular networks
Extent1 online resource (xl, 312 pages) : illustrations
DescriptionBoronic acid-substituted polymers are an attractive class of materials with broad potential applications in functional materials, chemo- and biosensors, as well as supported catalysts. In this work we present the synthesis of a new class of more electron-deficient borinic acid polymers, investigations into their use as catalysts in amide bond formation, and studies on their supramolecular assembly and polymer network formation.

We prepared two highly electron-deficient borinic acid copolymers, poly(styrene- co-2,4-dichlorophenyl borinic acid) and poly(styrene-co-3,5-dichlorophenyl borinic acid). The polymers and their corresponding model compounds, 2,4- and 3,5-substituted (dichlorophenyl)(tert-butylphenyl)borinic acid, were examined as catalysts in the amide bond formation reaction between phenylacetic acid and benzylamine. The 3,5- dichlorophenyl borinic acid derivatives proved to be the more effective catalysts. Mechanistic studies suggested that the borane Lewis acid-catalyzed coupling involves initial acid-induced protodeboronation to release dichlorophenyl boronic acid as the active catalyst. Furthermore, these borinic acid polymers are shown to form supramolecular assemblies via Lewis acid – Lewis base interactions and reversible covalent B-O-B bond formation. The dynamic processes were studied in detail by variable temperature (VT) NMR on the molecular model compounds and the respective pyridine-complexed boroxanes, R’RB-O-BRR’(Py).

In a second project, we investigated the use of borinic acid polymers in the formation of dynamic polymer networks with poly(dimethylsiloxane) (PDMS) as a soft and flexible component. These network polymers are crosslinked by boron-8- hydroxyquinolate moieties. We first prepared a series of model compounds by reaction of tBu- and 3,5Cl2-substituted (phenyl)(styrene)borinic acids (X = t-Bu and X = 3,5Cl2) with different 8-hydroxyquinoline ligands (8-hydroxyquinoline (HQ), 5-formyl-8- hydroxyquinoline (FHQ), 5-propylimino-8-hydroxyquinole (NHQ)) to study the dynamic nature of the B-O-C bonds in the presence of the quinoline nitrogen donor atom that is intramolecularly coordinated to the boron center. Six different boron-8-hydroxyquinolate complexes were used in exchange studies of free hydroxyquinolines with boron-bound hydroxyquinolines, as well as between different boron-bound hydroxyquinolines. Quantitative data on the thermodynamics of these exchange processes provide important insights into the expected dynamic processes in the supramolecular polymer networks. We then prepared polymer networks with chromophoric boron 8-hydroxyquinolate dynamic cross-links in the form of thin films by reacting 8-hydroxyquinoline-terminated PDMS with the borinic acid polymers. The resulted novel supramolecular polymer networks (SPNs) show an emergence of strong fluorescence due to formation of the fluorescent boron chelate complexes. We confirmed the SPN formation through 1H NMR studies and photophysical studies of the model complexes and the films.
NotePh.D.
NoteIncludes bibliographical references
Genretheses
Persistent URLhttps://doi.org/doi:10.7282/t3-89kh-f793
LanguageEnglish
CollectionGraduate School - Newark Electronic Theses and Dissertations
Organization NameRutgers, The State University of New Jersey
RightsThe author owns the copyright to this work.
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