Synthesis, Structural, Electrochemical, and DFT Studies of Highly Substituted Nonplanar Ni(II) Porphyrins and Their Intensity-Dependent Third-Order Nonlinear Optical Properties
Amir Sohel Bulbul, Albin Kuriakose, Komal, Reena Reena, Jitendra Nath Acharyya, G. Vijaya Prakash, Muniappan Sankar
Abstract
We designed and successfully synthesized highly substituted electron-deficient nonplanar Ni(II) porphyrins and their derivatives ( 1–7 ) in moderate to good yields. These derivatives were comprehensively characterized by various spectroscopic techniques and single-crystal X-ray diffraction (SCXRD) analysis. SCXRD analysis confirmed the structures of compounds 2, 4, and 7, adopting saddle-shape geometry. These nonplanar porphyrins demonstrated significant bathochromic shifts in their absorption spectra compared to parent NiTPP, attributed to the influence of bulky β -substituents and/or peripheral fusion. π-Extended porphyrins 6 and 7 displayed panchromatic absorption spectra extending into the NIR region. Porphyrins 6 and 7 demonstrated a profound anodic shift (∼400 mV) in their first reduction peak potentials compared to precursor NiTPP(NO 2 )Br 6 . The experimental absorption spectral pattern matches the simulated absorption spectra obtained from TD-DFT studies. The femtosecond laser intensity-dependent third-order nonlinear optical studies revealed that NiDFP(VCN) 2 Br 6 ( 6 ) and NiDFP(VCN) 2 (PE) 6 ( 7 ) displayed giant optical nonlinearities compared to the other porphyrins. Among all, NiDFP(VCN) 2 Br 6 ( 6 ) possessed the highest two-photon absorption coefficient ( β ) and cross-section (σ TPA ) values in the range of 22–33 × 10 –10 m/W and 3.77–6.95 × 10 6 GM, respectively. These findings suggest that the investigated nonplanar π-extended porphyrins are promising candidates for future optoelectronic applications.