Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes
| Main Author: | |
|---|---|
| Language: | English |
| Published: |
The Ohio State University / OhioLINK
2018
|
| Subjects: | |
| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=osu152570510019408 |
| id |
ndltd-OhioLink-oai-etd.ohiolink.edu-osu152570510019408 |
|---|---|
| record_format |
oai_dc |
| spelling |
ndltd-OhioLink-oai-etd.ohiolink.edu-osu1525705100194082021-08-03T07:06:47Z Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes Lanquist, Austin Paul Chemistry A series of five ruthenium polypyridyl complexes Ru(bpy)2P(PhR)3(CH3CN)]2+ triphenylphosphine derivative (R = OCH3, Me, H, F, CF3) have been synthesized and characterized in order to better understand the effect of changing electronic character has on the photodissociation of acetonitrile. Methods of characterization include 1H and 31P NMR, ESI-MS, cyclic voltammetry, fluorescence, and single crystal X-ray diffraction. Photolysis of this series exhibited a clean transition from reagent to photoproduct for all five complexes. Ru(bpy)2P(PhOMe)3(CH3CN)]2+ proved to be the most efficient at photosubsitution with a measured quantum yield of 0.76, exhibiting a 3-fold increase when compared to that of the weakest in the series, Ru(bpy)2P(PhCF3)3(CH3CN)]2+ with a quantum yield at 400nm of 0.26. Quantum yields were then compared with properties such as Hammett para substituents, phosphine pKa values, 31P-NMR signal, and HOMO-LUMO gap and found to trend exceedingly well. Discoveries herin prove that more effective photodynamic therapy reagents (PCT) can be synthesized by the addition of more electronic donating substituents. 2018-12-20 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu152570510019408 http://rave.ohiolink.edu/etdc/view?acc_num=osu152570510019408 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |
| collection |
NDLTD |
| language |
English |
| sources |
NDLTD |
| topic |
Chemistry |
| spellingShingle |
Chemistry Lanquist, Austin Paul Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes |
| author |
Lanquist, Austin Paul |
| author_facet |
Lanquist, Austin Paul |
| author_sort |
Lanquist, Austin Paul |
| title |
Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes |
| title_short |
Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes |
| title_full |
Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes |
| title_fullStr |
Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes |
| title_full_unstemmed |
Investigation of Ligand Electronic Effects on the Photodissociation of Acetonitrile from Ruthenium Polypyridyl Complexes |
| title_sort |
investigation of ligand electronic effects on the photodissociation of acetonitrile from ruthenium polypyridyl complexes |
| publisher |
The Ohio State University / OhioLINK |
| publishDate |
2018 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=osu152570510019408 |
| work_keys_str_mv |
AT lanquistaustinpaul investigationofligandelectroniceffectsonthephotodissociationofacetonitrilefromrutheniumpolypyridylcomplexes |
| _version_ |
1719454039494623232 |