Terrylenimides 3 and 4 represent a new class of blue colorants, exhibiting absorption maxima at 650 to 700 nm and fluorescence emissions in the NIR region (673 to 750 nm). The terrylenimides were synthesized by means of various organometallic coupling reactions, catalyzed by transition metal complexes (Ni(o) , Pd(o) ) and starting from the aromatic bromides, boronic acids, or organotin compounds. The terrylenimides have all the properties expected of excellent fluorescent dyes: high extinction coefficients, high fluorescence quantum yields, and very good thermal, chemical, and photochemical stabilities. Owing to its extended π system, 3 can reversibly accept four negative charges. By varying the substituents, 3 and 4 can be modified to serve either as soluble dyes or as insoluble pigments.

En route to highly colored chromophores, quaterrylenebis(dicarboximides) 1 were prepared, which can function both as pigments and soluble dyes. The polycycles absorb at very long wavelengths and are remarkably stable. R = H, R′ = C12H25; R = OC6H4‐p‐tBu, R′ = o,o′‐iPr2C6H3.

New ladder-type chromophores, the quaterrylenebis(dicarboxdiimide)s 2, 18 and 23, have been synthesised which, despite their extended p-system, exhibit good solubility in organic solvents and film forming properties when adequately substituted. These unprecedented dyes, which absorb and even emit light in the NIR window, are also characterized by oustanding chemical, thermal and photochemical stability with regard to their absorption range. The potential formation of J-aggregates in strongly acidic media has been investigated and has been ruled out by combined 1H NMR and UV-VIS-NIR spectroscopy experiments. In addition, their photophysical and electrochemical characteristics have been explored and are discussed. Results and discussionlenebis(dicarboximide)s, namely the terryleneimides 7,815 and Synthesis The synthetic pathway to quaterrylenebis(dicarboximide)s 2a,b †Chercheur Qualifie ´au Fonds National de le Recherche Scientifique, is illustrated in Scheme 1. The key building block for the synthesis Universite ´libre de Bruxelles, Chimie Macromole ´culaire, CP 206/1, of quaterrylenebis(dicarboximide)s is the N-substituted pery-Boulevard du Triomphe,