Near infrared two-photon-excited and -emissive dyes based on a strapped excited-state intramolecular proton-transfer (ESIPT) scaffold

Abstract

Fluorophores that can undergo excited-state intramolecular proton transfer (ESIPT) represent promising scaffolds for the design of compounds that show red-shifted fluorescence. Herein, we disclose new near infrared-emissive materials based on a dialkylamine-strapped 2,5-dithienylpyrrole as an ESIPT scaffold. The introduction of electron-accepting units to the terminal positions of this scaffold generates acceptor-π-donor-π-acceptor (A-π-D-π-A) type π-conjugated compounds. Following the ESIPT, the electron-donating ability of the core scaffold increases, which results in a substantially red-shifted emission in the NIR region, while increasing the oscillator strength. The electron-accepting units play a vital role to achieve intense and red-shifted emission from the ESIPT state. The strapped dialkylamine chain that forms an intramolecular hydrogen bond is also essential to induce the ESIPT. Moreover, an extended A-π-D-π-A skeleton enables two-photon excitation with the NIR light. One of the derivatives that satisfy these features, <i>i.e.</i>, borylethenyl-substituted <b>5</b>, exhibited an intense NIR emission in polar solvents such as acetone (<i>λ</i>_em = 708 nm, <i>Φ</i>_F = 0.55) with a strong two-photon-absorption band in the NIR region.