Tetra(5,6-dichloro-1,4-dithiacyclohexeno)tetraazaporphyrin H2TCTAP and its transition metal complexes MTCTAP( M = Mn(Ⅱ), Fe(Ⅱ), Ni(Ⅱ), Cu(Ⅱ)) have been synthesized by chlorization of chlorine-free tetraazaporphyrines, and characterized by elemental analysis, IR, and TG-DTA. H2TCTAP and MTCTAP are thermostable at 427 and 450℃, respectivily. Its electron spectra in DMF have been observed at -630 nm(Q band), 350 nm(B band), and at -460 nm(flu-orescence). Electron paramagnetic resonace spectra of the CuTCTAP powder at 77K have given anisotropic tensors g/...