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Synthesis and Photophysical Properties of Bipyridyl Pt(II) Bisstilbenylacetylide Complexes

This research explores the synthesis, photophysics, and nonlinear transmission properties of novel Bipyridyl Pt(II) bisstilbenylacetylide complexes. Emphasizing their unique photophysical characteristics, this study details the effects of substituents on stilbene, tuning of electronic states, and the potential applications in OLEDs, DNA intercalation, solar cells, photocatalysis, and nonlinear optical materials. The findings reveal a significant enhancement in two-photon absorption and charge transfer properties, showcasing the materials' promise for advanced photonic applications.

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Synthesis and Photophysical Properties of Bipyridyl Pt(II) Bisstilbenylacetylide Complexes

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  1. Bipyridyl Pt(II) Bisstilbenylacetylide: Synthesis, Photophysics, and Nonlinear Transmission Zhongjing Li Advisor: Professor Wenfang Sun Department of Chemistry and Biochemistry North Dakota State University

  2. Research Background • Intense interest in Pt(II) complexes • Unique photophysical properties • OLED, DNA intercalator, solar cells, photocatalysis, nonlinear optical materials • Pt(II) diiminebis(arylacetylide) complexes • Metal-to-ligand charge-transfer emissive state • HOMO and LUMO tuned by structure modification • Large σEX/σ0 in the visible region and large σTPA in the near-IR region Eisenberg, R. Inorg. Chem. 2000, 39, 447. Schanze, K. S. Inorg. Chem. 2001, 40, 4053. Castellano, F. N. Inorg. Chem. 2003, 42, 1394. Sun, W. Chem. Mater. 2010, 122, 6384.

  3. Bipyridyl Pt(II) Bisstilbenylacetylide • Combine the two photon absorption of stilbene with the excited-state absorption of platinum acetylide complex to obtain materials with broadband nonlinear absorption • Understand the effect of the substituent at the stilbene on the photophysics and nonlinear absorption of the complexes

  4. Electronic Absorption

  5. Ground-state MO Energy Diagram

  6. Photoluminescence

  7. Transient Absorption

  8. Nonlinear Absorption

  9. Unpublished results Two-Photon Absorptions

  10. Summary • The lowest-energy absorption bands and emission: • Dominated by the MLCT/LLCT with an admixture of the π,π* character in 3−5 • Dominated by the ligand-centered π,π* with the admixture of MLCT/LLCT characters in 1, 2, and 6 • Strong ns and fs TA in the visible spectral region from stilbene-localized π,π* state with the double bond in the trans geometry • Broad and extend to the near-IR region for 1 and 2: contribution from the acetylideligandcation • Strong RSA for the ns laser pulse at 532 nm, with complex 6 showing the strongest RSA

  11. Future Research • Platinum complexed based on cyclometallated tri-dentate ligands • Iridium complexes

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