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A two-step route to strongly absorbing and efficiently orange to deep red fluorescent, doubly B/N-doped, ladder-type pyrrolo[3,2- b ]pyrroles has been developed. We synthesize and study a series of derivatives of these four-coordinate boron-containing, nominally quadrupolar materials, which mostly exhibit one-photon absorption in the 500–600 nm range with the peak molar extinction coefficients reaching 150 000, and emission in the 520–670 nm range with the fluorescence quantum yields reaching 0.90. Within the family of these ultrastable dyes even small structural changes lead to significant variations of the photophysical properties, in some cases attributed to reversal of energy ordering of alternate-parity excited electronic states. Effective preservation of ground-state inversion symmetry was evidenced by very weak two-photon absorption (2PA) at excitation wavelengths corresponding to the lowest-energy, strongly one-photon allowed purely electronic transition. π-Expanded derivatives and those possessing electron-donating groups showed the most red-shifted absorption- and emission spectra, while displaying remarkably high peak 2PA cross-section ( σ 2PA ) values reaching ∼2400 GM at around 760 nm, corresponding to a two-photon allowed higher-energy excited state. At the same time, derivatives lacking π-expansion were found to have a relatively weak 2PA peak centered at ca. 800–900 nm with the maximum σ 2PA ∼50–250 GM. Ourmore »
Synthesis, photovoltaic performances and TD-DFT modeling of push–pull diacetylide platinum complexes in TiO 2 based dye-sensitized solar cellsIn this joint experimental–theoretical work, we present the synthesis and optical and electrochemical characterization of five new bis-acetylide platinum complex dyes end capped with diphenylpyranylidene moieties, as well as their performances in dye-sensitized solar cells (DSCs). Theoretical calculations relying on Time-Dependent Density Functional Theory (TD-DFT) and a range-separated hybrid show a very good match with experimental data and allow us to quantify the charge-transfer character of each compound. The photoconversion efficiency obtained reaches 4.7% for 8e (see TOC Graphic) with the tri-thiophene segment, which is among the highest efficiencies reported for platinum complexes in DSCs.