Synthesis and the spectral, electrochemical, and nonlinear optical properties of β-dicyanovinyl-appended ‘push–pull’ porphyrins

Abstract

A series of "push-pull" porphyrins, MTPP(MN)(TPA)₂ (M = 2H, Cu^II, Ni^II, and Zn^II), 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)₂ (M = 2H, Cu^II, Ni^II, and Zn^II) exhibited 21-48 nm and 38-80 nm bathochromic shifts in B and Q_<i>x</i>(0,0) bands as compared to the corresponding MTPPs (M = 2H, Cu^II, Ni^II, and Zn^II); 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 <i>Z</i>-scan technique to retrieve information about the nonlinear absorption and nonlinear refraction of the samples. The two-photon absorption coefficients (<i>β</i>) are in the range of 0.87 × 10^-13 to 4.28 × 10^-13 m W^-1 and the nonlinear refractive index (<i>n</i>₂) in the range of 1.21 × 10^-19 to 7.36 × 10^-19 m² W^-1. 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.