Giant Multi-Photon Absorption by Heptazine Organometalation

Multi-photon absorption (MPA) is of increasing interest for applications in technologically important "windows" of the electromagnetic spectrum (near-infrared III, NIR-III, 1550-1870 nm; and the new 2080-2340 nm region); however, few molecules exist that display strong MPA at these long wavelengths. We herein report the syntheses of the first 2,5,8-s-heptazine-cored organometallic complexes, together with organic analogues. The complexes exhibit outstanding 3PA cross-sections in the NIR-III and exceptional 4PA cross-sections in the new 2080-2340 nm window. We demonstrate that replacing organic donor groups by organometallic units results in an order of magnitude increase in 3PA, the "switching on" of 4PA, and a dramatic improvement in photo-stability. Our results highlight the impressive outcomes possible with an "organometalation" approach to NLO materials design.