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The role of electron acceptor/donor group substitution on the photophysical properties of tris(salicylideneanilines) (TSANs) was investigated. These compounds were synthesised and characterised through spectroscopic techniques including steady state absorption and emission spectroscopies. Their photochemical reaction mechanisms and properties were explored with the aid of ab initio methods of quantum chemistry. The obtained results allow us to verify the dependence of multiple emission bands on the substitution of electron donating and