Synthesis, vibrational spectroscopy and X-ray structural characterization of novel NIR emitter squaramides

Two new 2-naphthyl squaramides, 3-methoxy -4-(2-naphtalenylamino)-3-cyclobutene-1,2-dione (SQ-NPh1) and bis-3,4-(2-naphtalenylamino)-3-cyclobutene-1,2-dione (SQ-NPh2) were synthesized via condensation reaction between the dimethylsquarate and 2-naphthylamine. The spectrometric characterization by ¹³C NMR confirmed the obtaining of the squaramide derivative and nor the squaraine analog. This hypothesis was corroborated by Raman and Infrared spectroscopy since the characteristic vibrational bands related to the oxocarbon portion of both structures have been assigned, such as the ones for SQ-NPh1 and SQ-NPh2. The single-crystal X-ray crystallography for SQ-NPh1 crystal structures have been solved and the structure of SQ-NPh2 have been refined using Powder Diffraction state-of-art. The SQ-NPh1 crystallizes in monoclinic system in P2/c space group. Both squaramides present absorption in the ultra-visible (220-370 nm) and fluorescent emission in the near-infrared (780-800 nm), besides they also presented high thermal stability (around 570 °C). Generally, only squaraines are reported as NIR emitters, this is the first description of NIR emission for squaramides, and since the synthesis of squaramides is very easy and the rational design of small-molecule NIR fluorophores is of high priority and great value, these results are very promising for the development of novel NIR fluorescent dyes.