Synthesis and Photophysical Characterization of 1,6-bis(hydroxymethyl)pyrene
August Rothenberger, Andrew Cleek, Stephen Nagle, and Bratoljub Milosavljevic
Department of Chemistry, The Pennsylvania State University, University Park, PA 16802
Introduction
• Pyrene is a useful molecular probe due to its
excited state lifetime and excimer formation1
• Pyrene has low solubility in aqueous solution
(0.135mg/L), which limits its usefulness as a
probe to organic systems2
• 1-hydroxymethylpyrene has slightly higher
aqueous solubility by adding an –CH2OH group
• Aliphatic carbon partially preserves the
photophysical properties of pyrene
Intro
Fig. A&B. Structure of pyrene of 1-hydroxymethylpyrene
• Goal: Synthesize 1,6-bis(hydroxymethyl)
pyrene to determine if the addition of another
–CH2OH group will further improve the
aqueous solubility of the probe molecule
Synthethic Procedure
• 1,6-bis(hydroxymethyl)pyrene was
synthesized by a previously described route
from 1,6-dibromopyrene3
• Recovered a pale orange powder at a reaction
yield of 35.2%
Fig. C. Structure of
pyrene of 1,6-bis
-(hydroxymethyl)pyrene
Synthesis
• Characterized using IR spectroscopy
Fig. D. IR spectrum for
synthesized product.
Appearance of OH
stretching at 3283cm-1
indicates formation of
–CH2OH groups
• Further characterization performed using
photophysical data (see Figure 1)
Photophysicial Characterization Data
Figure 1. UV-Vis Absorbance Spectrum Figure 2. Fluorescence Emission Spectrum
Data
Preliminary results show 1,6-bis(hydroxymethyl)
pyrene to be less soluble in water than pyrene based
on absorbance data. The sparingly soluble solution
was purged with nitrogen gas and characterized.
Fig. 1. The primary absorbance peak shifts from 334nm
for pyrene to 341nm to 348nm as subsequent –CH2OH
groups were added, strongly suggesting the formation of
the correct synthetic product
Fig. 2. Fine structure degrades as –CH2OH groups are
added, signifying that the substituents electronically
interact with the aromatic electron cloud of pyrene
Fig. 3. Fluorescence decay rate of synthesized product is
Figure 3. Fluorescence Decay
very similar to pyrene and 1-hydroxymethylpyrene
Conclusions Acknowledgements
• 1,6-bis(hydroxymethyl)pyrene was We would like to thank Dr. Steven Weinreb for allowing us to use his
successfully synthesized and characterized by lab space and Steven Taylor for helping us carry out the synthesis. We
would also like to thank Rebecca Katz for her guidance throughout the
Acknowledgements
infrared and absorbance spectroscopy project. Finally, we would like to thank the Penn State Chemistry
• Preliminary data shows that the synthesized Department for providing additional lab space and instrumentation.
product is less soluble than pyrene in water
• The –CH2OH groups incrementally cause a
References
bathochromic shift in absorbance
• The –CH2OH groups incrementally destroy the References
1. K. Kalyanasundaram, J. K. Thomas. J. Am. Chem. 99 (7), 2039-2044 (1991).
2. National Center for Biotechnology Information. PubChem Compound
fluorescence fine structure of the probe Database; CID=31423, (accessed Dec 2, 2018).
3. G. D. Mulligan. Org. Prep. Proced. Int. 5(1), 37-39 (1973).