Potassium carbonate-promoted coupling reactions between 3-diazoindolin-2-imines and nucleophiles were tested. By respectively applying 2-naphthalenols and 2-arylacetates as nucleophiles, 3-azoindoles and 3-hydrazonoindolin-2-imines were obtained in excellent yields. Moreover, 3-azoindol-2-amines could be used as NNO pincer ligands for boron and resulted in the formation of hexacycleborofluorides with their absorption around 580 nm in dichloromethane.