Ionochromic Effects and Structures of Metalated Poly(p-phenylenevinylene) Polymers Incorporating 2,2′-Bipyridines

Lin X. Chen, Wighard J H Jäger, David J. Gosztola, Mark P. Niemczyk, Michael R Wasielewski

Research output: Contribution to journalArticle

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Abstract

The effects of metal ion chelation to the 2,2′-bipyridine (bpy) groups on the photophysics and exciton dynamics of two conjugated polymers 1 and 2 in solution are investigated. The structures of polymers 1 and 2 have 2,2′-bipyridyl-5-vinylene units that alternate with one and three 2,5-bis(n-decyloxy)-1,4-phenylenevinylene monomer units, respectively. The photophysics and exciton dynamics of metalated polymers 1 and 2 are compared to those of the metal-free polymers (Chen et al. J. Phys. Chem. A 1999, 103, 4341-4351). The origins of ionochromic effects due the metal ion chelation were studied using both steady-state and transient optical spectroscopy, and the results indicate that both conformational flattening and participation of π electrons from the metal in the π-conjugation of the polymer backbone play important roles in metal ion binding induced red shifts in absorption and photoluminescence spectra. The photoluminescence properties of the metalated polymers are determined by the metal ion electronic structures, where the closed shell Zn2+-bound polymer 2 has an increased photoluminescence quantum yield and the corresponding open shell Ni2+- or Fe3+-bound polymers have quenched photoluminescence due to spin-orbit coupling. The dual character of metalated polymer 2 as a conjugated polymer and as a metal-bpy complex is discussed. In addition, the structures of metal ion binding sites are studied via X-ray absorption fine structure (XAFS) and are related to the photophysical properties of the metalated polymers.

Original languageEnglish
Pages (from-to)1950-1960
Number of pages11
JournalJournal of Physical Chemistry B
Volume104
Issue number9
Publication statusPublished - Mar 9 2000

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Polymers
polymers
Metal ions
metal ions
Photoluminescence
Conjugated polymers
photoluminescence
Chelation
chelation
Excitons
Metals
Shells (structures)
poly(4-phenylenevinylene)
2,2'-Dipyridyl
excitons
metals
X ray absorption
Quantum yield
Binding sites
Metal complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Ionochromic Effects and Structures of Metalated Poly(p-phenylenevinylene) Polymers Incorporating 2,2′-Bipyridines. / Chen, Lin X.; Jäger, Wighard J H; Gosztola, David J.; Niemczyk, Mark P.; Wasielewski, Michael R.

In: Journal of Physical Chemistry B, Vol. 104, No. 9, 09.03.2000, p. 1950-1960.

Research output: Contribution to journalArticle

Chen, Lin X. ; Jäger, Wighard J H ; Gosztola, David J. ; Niemczyk, Mark P. ; Wasielewski, Michael R. / Ionochromic Effects and Structures of Metalated Poly(p-phenylenevinylene) Polymers Incorporating 2,2′-Bipyridines. In: Journal of Physical Chemistry B. 2000 ; Vol. 104, No. 9. pp. 1950-1960.
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