MESO/β-FUNCTIONALIZED PORPHYRINS AND CHLORINS: SYNTHESIS, SPECTRAL AND ELECTROCHEMICAL REDOX PROPERTIES AND THEIR UTILIZATION IN NLO, CATALYSIS AND SENSING

Abstract

describes a series of functionalized NiII monobenzoporphyrins (MBP) and chlorins (MBC) were synthesized and characterized by various spectroscopic techniques and electrochemical studies. One of the synthesized compounds, NiMBP(MN)2, was utilized as a chemodosimeter for selective naked-eye detection of cyanide ions in nonaqueous media via anion induced electron transfer (AIET). This processes afforded the π-extended vinyl cyanide appended porphyrin, NiMBP(VCN)2, which exhibits NIR absorptions and a narrow HOMO-LUMO gap of 1.47 V. Chapter 4 describes the synthesis and characterization of a new family of benzoporphyrin, MTPP(benzo)CHO [M = Zn(II) (1), 2H (2), Ni(II) (2a), Co(II) (2b) and Cu(II) (2c)] having an aldehyde (-CHO) group and a fused benzene ring at the antipodal positions. 2,3,12,13 Tetrachlorodibenzoporphyrinatonickel(II) (3) has been synthesized and characterized. 4.6 Abs. 4.1 3.6 1/[A0-A] 3.1 2.6 2.1 1.6 r² = 0.979 3E+09 2E+09 1E+09 0 1/[CN-]2 M = Zn(II) (1), 2H (2), Ni(II) (2a), Co(II) (2b) & Cu(II) (2c) Wavelength (nm) NiTPP(Benzo)2Cl4 (3) the 0.58-1.25 NiTPP(Benzo)2Cl4 0.17 0.44 1.02 NiTPP(Benzo)2-1.08 Abs. 2.1 1.9 1/[A0-A] R² = 0.9963 1.7 12000 22000 32000 42000 1/[CN-]2 Potential (V) Wavelength (nm) All these benzoporphyrins exhibited a significant red-shift in the Soret band as compared to the precursor along with tunable redox properties. They have shown saddle nonplanar conformation of macrocyclic core confirmed by DFT calculation and single-crystal XRD.