Synthesis and Characterization of New Self-Assembled Metallo-Polymers Containing Electron-Withdrawing and Electron-Donating Bis(terpyridine) Zinc(II) Moieties
-
Schluetter, Florian; Wild, Andreas; Winter, Andreas; Hager, Martin D.; Baumgärtel, Anja; Friebe, Christian; Schubert, Ulrich S.
- Abstract:
- A series of rigid π-conjugated bis(terpyridines) (M1-M7) bearing electron-acceptor spacer
units in 40-position was synthesized in moderate to high yields by Pd0-catalyzed Sonogashira cross-coupling
reactions. The compounds were fully characterized by NMR spectroscopy, MALDI-TOF mass spectrometry,
elemental analysis and their photophysical properties were discussed in detail. These new bis-
(terpyridines) were applied for the self-assembly reaction with ZnII ions to form metallo-homo polymers
(P1-P7). Broadened NMR signals and UV-vis titration experiments confirmed the successful polymerization.
The electro-optical properties of the materials were investigated in detail. Band gaps up to 2.08 eV and
bright blue to orange photoluminescence with quantum yields of 18 to 66% were observed strongly
depending on the nature of the π-conjugated bis(terpyridine) system. In combination with electron-donor
ditopic terpyridine ligands (MD1 and MD2), two ZnII random copolymers (R1 and R2) were synthesized.
These materials were investigated by UV-vis absorption and photoluminescence experiments in dilute
solution and in the solid state, prepared by spin-coating from DMF solutions. Thereby, random copolymer
R2 featured an energy transfer from the donor to the acceptor part in dilute solution.
- Year:
- 2010
- Type of Publication:
- Article
- Journal:
- Macromolecules
- Volume:
- 43
- Pages:
- 2759 - 2771