Photophysical properties of an array of various polyaromatic hydrocarbons were benchmarked with B3LYP, M06 and B97D methods coupled with Pople and CEP-31G(d) basis sets. Results from the benchmark show the importance of diffuse basis sets when modeling the electronic properties of highly conjugated systems and provide qualitative reliable accuracy with certain levels of theory. B97D and M06 are applied to modeling pyrene adducts governed by non-covalent interactions in both gaseous and condensed states to reproduce experimental spectra. DFT calculations with both B97D and M06 functionals show qualitatively and quantitatively that pyrene dimer is a stronger π–base as compared to its monomer. Binding energies coupled with MEP, PCA and Qzz results show that the difference in π-basicity of the monomer and dimer impacts the supramolecular chemistry involved in adducts formed with super π-acidic silver cyclometallic trimer (CTC). Non-covalent interactions between coinage metal CTCs and ammonia/phosphine substrates is reported. Interactions between these substrates and the facial plane of the π-rich gold CTC reveal a novel interaction, where the typical Lewis acid/base roles are reversed for the substrates. Adducts formed through this type of interaction define typical Lewis bases like ammonia and phosphine as Lewis acids, wherein the partially positive hydrogens coordinate to the metallo-aromatic center through dipole-quadrupole interactions. Interactions of ammonia at the side positions is shown to heavily impact the Lewis basicity of the CTC facial plane leading to similar interactions exhibited by the ammonia-gold CTC adducts. Structural and electronic properties of the adducts modeled are examined.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc1609127 |
| Date | 12 1900 |
| Creators | Williams, Christopher M. |
| Contributors | Cundari, Thomas, Marpu, Sreekar, D'Souza, Francis, Yang, Chi, Slaughter, LeGrande M. |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | xii, 97 pages, Text |
| Rights | Use restricted to UNT Community, Williams, Christopher M, Copyright, Copyright is held by the author, unless otherwise noted. All rights Reserved. |
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