Synthesis and the spectral, electrochemical, and nonlinear optical properties of β-dicyanovinyl-appended 'push-pull' porphyrins.

A series of "push-pull" porphyrins, MTPP(MN)(TPA) (M = 2H, Cu, Ni, and Zn), having triphenylamine (TPA) and dicyanovinyl (DCN) groups at antipodal positions were synthesized and characterised by UV-Vis, fluorescence and NMR spectroscopic techniques, MALDI-TOF mass spectrometry, cyclic voltammetry, DFT, and elemental analysis, which were then further utilized for third-order nonlinear optical measurements under mild conditions using femtosecond laser pulses. Remarkably, MTPP(MN)(TPA) (M = 2H, Cu, Ni, and Zn) exhibited 21-48 nm and 38-80 nm bathochromic shifts in B and Q(0,0) bands as compared to the corresponding MTPPs (M = 2H, Cu, Ni, and Zn); the results are consistent with the effect of enhanced resonance due to TPA and -I effect of DCN moieties. In cyclic voltammetry, the push-pull porphyrins exhibited a cathodic shift (0.13-0.51 V) in their first oxidation potential as compared to the precursor owing to the presence of electron-donating TPA groups. The third-order nonlinear optical responses were recorded using a single-beam femtosecond -scan technique to retrieve information about the nonlinear absorption and nonlinear refraction of the samples. The two-photon absorption coefficients () are in the range of 0.87 × 10 to 4.28 × 10 m W and the nonlinear refractive index () in the range of 1.21 × 10 to 7.36 × 10 m W. The ultrafast absorption dynamics of the ground-state bleaching (GSB) and photo-induced absorption (PIA) are monitored by femtosecond broadband transient absorption studies. The strong nonlinearity of these push-pull porphyrins makes them potential candidates for nonlinear optical and photonic device applications.