Two new ligands, S-benzyl-b-N-[10-ethylphenothiazine-3-methylene] dithiocarbazate (HL1), S-methyl-b-N-[10-ethylphenothiazine-3-methylene] dithiocarbazate (HL2), and their complexes 122222(ZnL, ZnL, CdL), which exhibit intensive two-photon excited (TPE) fluorescence at 800 nm laser pulses in the femtosecond regime, are synthesized and fully characterized. The measured power dependence of the fluorescence signals provides a direct evidence for TPE. All of them exhibit a large two-photon absorptive crosssection. The two-photon-excited fluorescence spectra of them are compared and contrasted with the corresponding results obtained from the one-photon excitation. Emission peaks of the ligands and their complexes are observed mostly at the region 550—595 nm in the TPE fluorescence spectra.
The synthesis, luminescence and electrochemical properties of two novel phenothiazine derivatives were presented, which exhibit good one-photon fluorescence emission. The quantum yields and solvent effects of them were studied in detail. Compound 3,7-bis（2-4＇-imidazolylbenzylidenehydrazonoethyl）-（0-ethylphenothiazine） （5） was used as an effective initiator, of which two-photon fluorescence spectra were investigated under 800 nm fs laser pulse and the measured two-photon absorption cross-section was 18 × 10^-50 cm^4·s per photon. Two-photon initiated polymerization microfabrication experiments were carried out. X-ray diffraction analyses revealed that the shape of the compound 3,7-bis（2-pyrid-4＇-ylmethylidenehydrazonoethyl）-（0-ethylphenothiazine） （4） looks like a butterfly with nearly planar wings. The dihedral angle of the two benzene rings is 37.6° and there is an obvious π-π stacking interaction between the molecules in the crystal.
