6 March 2013 Modified p-phenylene vinylene platinum (II) acetylides with enhanced two-photon absorption in solid host
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Organometallic complexes comprising of a platinum (II) acetylide core linked with different -conjugated chromophores are promising materials for applications requiring strong nonlinear-optical response. In dual-mode optical power limiting, the chromophore first undergoes ultrafast two-photon absorption (2PA) in singlet manifold, followed by efficient intersystem crossing (ISC) and subsequent T-T absorption. While the heavy atom facilitates efficient T-T absorption, achieving sufficiently high intrinsic 2PA cross-section value has remained an issue. Here we present a series of linear- and cross-conjugated p-phenylene vinylene platinum (II) acetylides (TPV1-Ph, TP01-TPV2, crossTPV1, crossTPV1-DPAF, crossTPV3) with extended π-conjugated chains and discuss their linear- and nonlinear photophysical properties, including comparison to the properties of the constituting ligand chromophores. Remarkably high femtosecond 2PA cross-section values (up to 10,000 GM) were obtained for several of the new complexes by both nonlinear transmission (NLT) and two-photon excited fluorescence (2PEF) method. The large 2PA values, especially in crossTPV1 and crossTPV3, span a broad range of wavelengths, 570 – 810 nm, which overlaps with maximum wavelength of strong T-T excited state absorption measured by nanosecond transient absorption method. This combination of properties renders these compounds efficient dual-mode nonlinear absorbers in the visible to near-IR region. Examination of the photophysical properties allows us to elucidate the structure-property relationships both in the solutions as well as in solid samples where the chromophores are incorporated into a polymer host.
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Galyna G. Dubinina, Galyna G. Dubinina, Randi S. Price, Randi S. Price, Geoffrey Wicks, Geoffrey Wicks, Pawel Wnuk, Pawel Wnuk, Yuriy Stepanenko, Yuriy Stepanenko, Mikhail Drobizhev, Mikhail Drobizhev, Aleksander Rebane, Aleksander Rebane, Kirk S. Schanze, Kirk S. Schanze, "Modified p-phenylene vinylene platinum (II) acetylides with enhanced two-photon absorption in solid host", Proc. SPIE 8622, Organic Photonic Materials and Devices XV, 86220I (6 March 2013); doi: 10.1117/12.2004180; https://doi.org/10.1117/12.2004180

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