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Unsymmetrical metal-free and zinc complexes of pyrazinoquinoxalino-porphyrazines (PQP) bearing eight diethylamino groups have been synthesized by statistical tetramerization of 2,3-bis(diethylamino)quinoxaline-6,7-dicarbonitrile and 5,6-bis(diethylamino)pyrazine-2,3-dicarbonitrile in lithium butanolate. For this purpose, a new heteroatom-substituted quinoxaline precursor, 2,3-dichloro-6,7-dicarbonitrile, was prepared and characterized. It is a flexible starting material for new building blocks of quinoxaline-6,7-dicarbonitrile derivatives. All the PQPs (including adjacent and opposite isomers) from the statistical mixture were detected and separated by column chromatography on silica and characterized