Azulene-Substituted Donor-Acceptor Polymethines and 1,6'-Bi-, 1,6';3,6''-Ter-, and Quinqueazulenes via Zincke Salts: Synthesis, and Structural, Optical, and Electrochemical Properties.

Abstract

Azulene-substituted donor-acceptor polymethines, bi-, ter-, and quinqueazulenes composed of the 1,6'-biazulene unit have been successfully prepared from corresponding Zincke salts. The synthesis of polymethines through the reaction of Zincke salts with several amines, followed by a Knoevenagel reaction with malononitrile, was accomplished in moderate to high yields (40-92 %). Meanwhile, the reaction of Zincke salts with secondary amines and the subsequent sequential condensation-cyclization with cyclopentadienide ions, so-called Ziegler-Hafner method, produced the corresponding 1,6'-biazulenes, 1,6';3,6''-terazulenes, and quinqueazulene, respectively. The structural, optical, and electrochemical properties of the azulene-substituted donor-acceptor polymethines, bi-, ter-, and quinqueazulenes were revealed by single-crystal X-ray structure analysis, UV/vis spectroscopy, voltammetry analysis, spectroelectrochemistry, and theoretical calculations. These results suggested that the substituents on the azulene ring and their substitution positions directly affect their reactivities, optical and electrochemical properties.