Document Type
Honors Project
Publication Date
6-13-2025
Abstract
Through this project, computational tools were refined to be more rigorous and robust for the primarily synthetic SazLab at Lawrence University. The primary research of the SazLab involves synthesizing and characterizing luminescent radicals based on two stable radical systems: TTM and BDPA. The BDPA system is of particular interest because the effects on luminescence of its nonalternant symmetry are less understood compared to the alternant symmetry of TTM. Quantum mechanical calculations, particularly Density Functional Theory, were utilized to help target syntheses and gain insight into the photophysics of luminescence. A prior student researcher with the SazLab had successfully synthesized 2-pyBDPA, BDPA with a pyrene substituent attached externally in the 2-fluorene position, but that sample does not appear to luminesce. To further investigate the pyBDPA system, a computational experiment was designed to test the oscillator strengths of the D1 bright state transition for 7 unique variations of pyBDPA. This was done to gauge the probability of initial absorption into the D1 excited state. Through the experiment, it was revealed that 2-pyBDPA has the lowest oscillator strength of all 7 pyBDPA variations. This was an intriguing result, as it provided a reasonable explanation to our observations that 2-pyBDPA luminesces very little, if at all. Additionally, it was found that moving pyrene one position over to the 3-fluorene position predicted the highest oscillator strength by far, more than 20 times that of 2-pyBDPA. This result provided the SazLab a new synthesis target to investigate, as development of synthesis methods for 3-pyBDPA is now in progress. Excited state calculations are also in progress to characterize the D1 excited state. Our ultimate goal is to understand the underlying structure-function relationship of the position and integration of luminophores on BDPA, and what effects that has on luminescence.
Level of Honors
cum laude
Department
Chemistry
Advisor
Graham Sazama
Recommended Citation
Piwoni, Samantha Kristine, "Predicting the Photophysics of BDPA-based Radicals Using Density Functional Theory" (2025). Lawrence University Honors Projects. 211.
https://lux.lawrence.edu/luhp/211
Predicting the Photophysics of BDPA-based Radicals Using Density Functional Theory - Supplemental Material