Thermochromism of a Poly(phenylene vinylene): Untangling the Roles of Polymer Aggregate and Chain Conformation
We report reversible thermochromism of a conjugated polymer, poly{l_brace}2,5-bis[3-(N,N-diethylamino)-1-oxapropyl]-1,4-phenylenevinylene{r_brace} (DAO-PPV), in diluted solutions of toluene and 1,2-dichlorobenzene. By means of temperature- and solvent-dependent steady-state spectroscopy, picosecond time-resolved photoluminescence spectroscopy, and dynamic light scattering, we provide new insights into the role of polymer aggregates in defining the thermochromic behavior of PPVs. We find DAO-PPV to exhibit a low temperature state with vibronically structured red visible absorption and emission spectra. Structurally, this low temperature state is a densely packed and disordered polymer aggregate, which contains a fraction of well-ordered, packed polymer chains. These ordered regions serve as low energy trap sites for the more disordered regions in the aggregate, thus regulating the final emission of the aggregate and imposing a vibronically resolved emission spectrum, which is usually associated with emission from one or a few chromophores. The high temperature state of DAO-PPV is a loose aggregate, with structureless absorption and emission spectra in the green visible range. Structurally, the loose aggregate is a well-solvated aggregate retaining the physical dimension of the dense aggregate but for which interchain interactions are diminished with the increase of temperature. As a result, the spectroscopic behavior of the loose aggregate is very similar if not identical to that of the single polymer chain. Increased solubility untangles polymer aggregates into single, dispersed, polymer chains, as we demonstrate here for DAO-PPV in 1,2-dichlorobenzene and at high temperature.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE SC OFFICE OF SCIENCE (SC)
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1040293
- Report Number(s):
- BNL-90993-2010-JA; R&D Project: NC-001; KC020401H; TRN: US201210%%471
- Journal Information:
- Journal of Physical Chemistry B, Vol. 113, Issue 50; ISSN 1520-6106
- Country of Publication:
- United States
- Language:
- English
Similar Records
Solid-state-concentration effects on the optical absorption and emission of poly({ital p}-phenylene vinylene)-related materials
Polarized electroabsorption spectroscopy of highly ordered poly(2-methoxy,5-(2{prime}-ethyl-hexoxy)-{ital p}-phenylene vinylene)