A new family of salphen based complexes, viz. Zn(salphenazine)s, has been prepared and is characterized by a larger π-surface compared to previously reported Zn(salphen) complexes. The spectroscopic properties of these Zn(salphenazine)s have been studied in detail using UV-Vis and fluorescence spectroscopy, and further investigated by computational methods. The first application of a Zn(salphenazine) complex in a small molecule organic solar cell (smOSC) is presented showing the potential of salphenazine systems in this area.