Res. Chem. Intermed.
, Vol. 33, No. 1–2, pp. 125–142 (2007)
©
VSP 2007.
Also available online - www.brill.nl/rci
Ionic strength and solvent control over the physical
structure, electronic properties and superquenching of
conjugated polyelectrolytes
ALEX D. SMITH, CLIFTON KWANG-FU SHEN
∗
, SEAN T. ROBERTS
∗∗
,
ROGER HELGESON and BENJAMIN J. SCHWARTZ
∗∗∗
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA
90095-1569, USA
Received 27 March 2004; revised 8 June 2004
Abstract—In this paper, we investigate the photophysical properties of the conjugated polyelectrolyte
poly(2-methoxy-5-propyloxy sulfonate phenylene vinylene) (MPS-PPV), dissolved in both water
and DMSO as a function of the solution ionic strength. Dynamic light scattering indicates that
MPS-PPV chains exist in a highly agglomerated conformation in both solvents, and that the size of the
agglomerates depends on both the ionic strength and the charge of the counter-ion. Even though the
degree of agglomeration is similar in the two solvents, we find that the fluorescence quantum yield of
MPS-PPV in DMSO is nearly 100-times greater than that in water. Moreover, intensity-dependent
femtosecond pump-probe experiments show that there is a significant degree of exciton–exciton
annihilation in water but not in DMSO, suggesting that the MPS-PPV chromophores interact to form
interchain electronic species that quench the emission in water. Given that the emission quenching
properties depend sensitively on the chain conformation and degree of chromophore contact, we
also explore the superquenching properties of MPS-PPV in the two solvents as a function of ionic
strength. We find that superquenching may be either enhanced or diminished in either of the solvents
via addition of simple salts, and we present a molecular picture to rationalize how the conformational
properties of conjugated polyelectrolytes can be tuned to enhance their emissive behavior for sensing
applications.
Keywords: Poly(2-methoxy-5-propyloxy sulfonate phenylene vinylene); photophysical properties;
superquenching; ionic strength; solvent control; fluorescence; femtosecond pump-probe experiments.
*
Present address: Department of Chemistry, Northwestern University, Evanston, IL 60208-3113,
USA.
**
Present address: Department of Chemistry, Massachusetts Institute of Technology, Cambridge,
MA 02139-4307, USA.
***
To whom correspondence should be addressed. E-mail: schwartz@chem.ucla.edu