UROP Research Mentor Project Submission Portal: Submission #322

Submission information
Submission Number: 322
Submission ID: 7856
Submission UUID: 4f59305f-10d1-43fc-a7d9-4708362583fa

Created: Wed, 05/31/2023 - 01:08 PM
Completed: Wed, 05/31/2023 - 04:58 PM
Changed: Mon, 08/21/2023 - 10:48 AM

Remote IP address: 128.186.109.118
Submitted by: Anonymous
Language: English

Is draft: No
Primary Research Mentor Name Jack Saltiel
Research Mentor Preferred Pronouns
When potential research assistants are reaching out via email, what is your preferred honorific? Dr.
Contact Email (FSU Email if affiliated) jsaltiel@fsu.edu
Position Title Faculty
FSU College (if applicable) Arts and Sciences
FSU Department or Non-FSU Organization Affiliation Chemistry and Biochemistry
Headshot (optional) Jack Saltiel_10-6-17.jpg
Research Assistant Supervisor (if different from above) Sumesh Babu Thomas
Research Assistant Supervisor Preferred Pronouns
Research Assistant Supervisor Preferred Honorific? Dr.
Contact Email (FSU Email if affiliated)
Name of Other Faculty/Collaborator(s) (if applicable) Edwin Hilinski
Other Faculty/Collaborator(s) Preferred Pronouns
Other Faculty/Collaborator(s) Preferred Honorific? Dr.
Contact Email (FSU Email if affiliated) hilinski@chem.fsu.edu
Title of the Project The Photoaddition of Alcohols to Methoxy Substituted Stilbenes
Project Keywords Trapping the Phantom Excited Singlet State
Are you currently looking for research assistants? Maybe one more
Number of Research Assistants Needed 2
Relevant Research Assistant Major(s) Prefer Chemistry majors interested in graduate school.
Project Location: On FSU Main Campus
If the project location is off campus, does the research assistant(s) need to provide their own transportation? Yes
Please select the choice that most accurately describes your expectations for the research assistant(s): In-person
Approximately how many hours a week would the research assistant(s) need to work? At least 10 hours/week
Roughly what time frame do you expect research assistant(s) to work? Flexible schedule (Combination of business and outside of business. TBD between student and research mentor.)
Overall Research Project Description UROP Project Saltiel Laboratory
The Mechanism of Ether Formation from the Photoaddition of Alcohols to p- and m-Methoxystilbenes
The photoaddition of methanol, ethanol and 2,2,2-trifluoroethanol (TFE) to methoxy-substituted stilbene derivatives was described by Roberts and Pincock. [1] The position of the methoxy group was shown to have an enormous effect on the fluorescence efficiency (quantum yield, QYf) of the stilbene. [2] Measured fluorescence yields in acetonitrile are 0.007 and 0.16 for t-p-MeOSt and t-m-MeOSt, respectively, Chart 1. [2] TFE quenches the fluorescence of the trans-isomers and they concluded that this was due to protonation of the trans-stilbene singlet excited states (1t*). The resulting cations react with the alkoxide ion to give ether by coupling, or bibenzyl products by hydride transfer. [2] Ether also forms following rearrangement to a carbene intermediate. [1-4] Our more recent work with the unsubstituted stilbenes established that the major protonation pathway follows torsional relaxation of 1t* to a common zwitterionic twisted intermediate, 1p* that is also accessed from the cis-stilbene singlet excited state, 1c*. [3] The mechanism is shown for deuterated methanol in Scheme 1. Consequently, we have questioned Pincock’s conclusion that protonation precedes torsional relaxation. [3] Studying the initial formation of the ethers starting from the pure trans- and cis-isomers of p-MeOSt and m-MeOSt will allow evaluation of the degree to which ether formation involves 1t* or 1p*.
References
(1) Roberts, J. C.; Pincock, J. A. The Photochemical Addition of 2,2,2-Trifluorethanol to Methoxy-Substituted Stilbenes. J. Org. Chem. 2004, 69, 4279-4282.
(2) Roberts, J. C.; Pincock, J. A. Methoxy-substituted stilbenes, styrenes, and 1-arylpropenes: Photophysical properties and photoadditions of alcohols. J. Org. Chem. 2006, 71, 1480-1492.
(3) Saltiel, J.; Gupta, S. Photochemistry of the Stilbenes in Methanol. Trapping the Common Phantom Singlet State. J. Phys. Chem. A 2018, 122, 6089-6099. Woning, J.; Oudenampsen, A.;
(4) Laarhoven, W. H. Photochemical Addition of Methanol to Stilbenes. J. C. S. Perkin Trans. 2 1989, 2147-2154.
Research Tasks The undergraduate research project consists of securing the pure trans-isomers of p-MeOSt and m-MeOSt and synthesizing the cis-isomers using triplet sensitized photoisomerization followed by column liquid phase chromatography. Addition of alcohols in parallel to the two pairs of isomers will be carried out in a Merry-Go-Round apparatus and the progress of photoisomerization and ether formation will be determined by gas phase chromatography using a flame ionization detector. Products will be separated by liquid chromatography and their purity will be determined by 1H NMR and UV spectroscopies. This research should determine whether the mechanism in Scheme 1 applies to the methoxy-substituted stilbenes.
Skills that research assistant(s) may need: Having had the CHM 2210 and 2211 Organic Chemistry courses would help.
Mentoring Philosophy I have had some 135 undergraduate students carry out research in my laboratory. See DOI: 10.1021/acscentsci.9b00841 for the evaluation of my mentoring by one of these students.
Please provide a link to your publications, a video clip, or a website for your research project (if applicable): https://www.chem.fsu.edu/~jsaltiel/
Please add any additional information here (if applicable): In the project description Chart 1 and Scheme 1 were omitted. Please email me if you wish to see a pdf document that includes them.
Mentor Handbook, FAQs, and Communication Yes
UROP Performance Evaluation Yes
Materials Grant Yes
UROP Poster Presentation Yes
Year 2023
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