2(3),9(10),16(17),23(24)-Tetrakis(dibutylamino)-phthalocyanine compounds M{Pc[N(C4H9)(2)](4)} (1-5; M = 2H, Mg, Ni, Cu, Zn) were prepared and characterized by a range of spectroscopic methods in addition to elemental analysis. Electrochemical and electronic absorption spectroscopic studies revealed the more effective conjugation of the nitrogen lone pair of electrons in the dibutylamino side chains with the central phthalocyanine pi system in M{Pc[N(C4H9)(2)](4)} than, in M{Pc[N(C4H9)(2)](8)}, which, in turn, results in superior third-order nonlinear-optical (NLO) properties of H-2{Pc[N(C4H9)(2)](4)} (1) over H-2{Pc[N(C4H9)(2)](8)}; as revealed by the obviously larger effective imaginary third-order molecular hyperpolarizability (Im{x((3))}) of. 6.5 x 10(-11) esu for the former species than for the latter one with a value of 3.4 x 10(-11) esu. This is well rationalized on the basis of both structural and theoretical calculation results. The present result seems to represent the first effort toward directly connecting the peripheral functional substituents, electronic structures, and NLO functionality together for phthalocyanine molecular materials, which will be helpful for the development of functional phthalocyanine materials via molecular design and synthesis even through only tuning of the peripheral functional groups.