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Unhindered Triangulene Salt Pairs: Substitution-Dependent Contact Ion Pairing And Complex Solvent-Separated Discotic Ions In Solution, Subrahmanyam Modekrutti

Theses and Dissertations--Chemistry

This work sought to enforce aromatic interactions between compatible π-molecular orbital systems with ionic bonding. In this case the interacting partners are oppositely charged discotic triangulene derivatives. The observed properties of the heterodimeric ion-pairs likely arise due to a hypothetical synergy between electrostatics and π-interactions. The work presented here describes investigation of putative covalency arising from this hypothetical synergy in the electrostatics driven π-stacking. In order to probe this, various hypotheses were made and experiments were designed to test their validity. The results from the experiments show existence of contact ion-pairs and complex solvent-separated discotic ions in solution. The formation …

Spectroscopic Characterization Of Lanthanum-Mediated Hydrocarbon Activation, Dilrukshi C. Hewage

Theses and Dissertations--Chemistry

Lanthanum (La)-promoted hydrocarbon activation reactions were carried out in a laser vaporization metal cluster beam source. Reaction products were identified by time-of-flight mass spectrometry, and the approximate ionization thresholds of La-hydrocarbon complexes were located with photoionization efficiency spectroscopy. The accurate ionization energies and vibrational frequencies of the La complexes were measured using mass analyzed threshold ionization (MATI) spectroscopy. Their molecular structures and electronic states were investigated by combing the MATI spectroscopic measurements with quantum chemical and Franck-Condon factor calculations.

In this dissertation, La-mediated C-H and C-C bond activation reactions were investigated for several small alkynes (acetylene, propyne) and alkenes (propene, …