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A series of “push–pull” porphyrins, MTPP(MN)(TPA)2 having triphenylamine (TPA) and dicyanovinyl (MN) at antipodal positions were synthesized and characterized. They were utilized for third-order nonlinear optical measurements using kHz laser pulses.

A new series of "push-pull"meso-substituted trans-A

Two new series of β-triphenylamine-appended porphyrins (MTPP(TPA)2X, (where M = 2H, Co(II), Ni(II), Cu(II), Zn(II) and X = NO2/CHO) have been synthesized and characterized by various spectroscopic techniques, namely, UV-vis, fluorescence, NMR spectroscopy, mass spectrometry, cyclic voltammetry, density functional theory and ultrafast nonlinear optical (NLO) studies. They exhibited 16–22 nm and 39–58 nm red-shifts in the Soret and Qx(0,0) bands, respectively, as compared to MTPPs due to the resonance and inductive effects of β-substituents on the porphyrin π-system. The first reduction potential of CuTPP(TPA)2NO2 and CuTPP(TPA)2CHO exhibited an anodic shift by 0.44 and 0.36 V, respectively, as referenced to CuTPP, due to the electronic nature of β-substituents (NO2 and CHO), which led to their easier reduction compared with CuTPP. H2TPP(TPA)2NO2 and H2TPP(TPA)2CHO exhibited the largest resultant dipole moments (7.66 D and 4.55 D, respectively) as compared to H2TPP (0.052 D) due to the cross-polarized push–pull effect of β-substituents (NO2/CHO and triphenylamino groups) and the nonplanarity of the macrocyclic core. Third-order nonlinear optical properties of MTPP(TPA)2NO2 and MTPP(TPA)2CHO (M = 2H and Zn(II)) were investigated in a broad spectral range (680–850 nm) using the Z-scan technique with femtosecond 80 MHz pulses. These materials demonstrate strong nonlinear optical coefficients, endowing them with potential for prominent photonic applications.

Mixed substitution at the β-position of porphyrins influences their photophysical and electrochemical redox properties. Two new series of asymmetrically mixed β-octasubstituted porphyrins viz. MTPP(Ph)2Br5X (X = NO2 or Br and M = 2H, Co(ii), Ni(ii), Cu(ii), and Zn(ii)) have been synthesized and characterized by various spectroscopic techniques. The single crystal X-ray structure of H2TPP(NO2)(Ph)2Br5 showed a nonplanar saddle shape conformation of the macrocyclic core. Furthermore, the fully optimized geometries confirmed the saddle shape conformation of H2TPP(Ph)2Br5X (X = NO2 or Br). Electronic spectra revealed a significant bathochromic shift by appending both electron donor and acceptor substituents at the β-position of the meso-tetraphenylporphyrin skeleton, which reflects the following order H2TPP < H2TPP(NO2) < H2TPP(NO2)(Ph)2 < H2TPP(Ph)2Br6 < H2TPP(NO2)(Ph)2Br5. H2TPP(Ph)2Br5X (X = NO2 or Br) exhibited a significant bathochromic shift (Δλmax = 53-61 nm) in the Soret band and (Δλmax = 90-95 nm) in the longest wavelength Qx(0,0) band as compared to H2TPP. Nonplanar conformations and electron withdrawing β-substituents induce higher protonation and deprotonation constants for H2TPP(NO2)(Ph)2Br5 and H2TPP(Ph)2Br6 as compared to precursor porphyrins viz. H2TPP, H2TPP(NO2) and H2TPP(NO2)(Ph)2. The electronic spectral properties and redox potentials of MTPP(Ph)2Br5X (X = NO2 or Br and M = 2H, Co, Ni, Cu and Zn) are affected by β-substituents at the periphery of the porphyrin core. Redox tunability was achieved by appending push-pull substituents at the β-position of the MTPP (M = 2H, CoII, NiII, CuII, and ZnII) skeleton of the macrocycle. CuTPP(Ph)2Br6 and CuTPP(NO2)(Ph)2Br5 exhibited a dramatically reduced HOMO-LUMO gap with a difference of 0.55 V and 0.62 V, respectively as compared to CuTPP due to the push-pull effect of β-substituents and nonplanarity of the porphyrin core.

β-Functionalization of meso-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin with electron acceptors such as formyl and dicyanovinyl has been reported for the first time. 2-Formyl-5,10,15,20-tetrakis(3',5'-di-tert-butyl-4'-hydroxyphenyl)porphyrinatocopper(ii) (Cu-TDtBHPP-CHO) crystallizes in the triclinic space group P1[combining macron], [a = 10.8479(4) A, b = 14.6207(5) A, c = 15.9745(5) A, V = 2198.97(13) A3] and exhibits an almost planar structure and a square planar geometry. β-Formyl/dicyanovinyl substituted porphyrins such as Cu-TDtBHPP-CHO, Ni-TDtBHPP-CHO, Cu-TDtBHPP-MN (1), Ni-TDtBHPP-MN (2) and H2-TDtBHPP-MN (3) exhibited red-shifted optical absorption features (Δλmax = 13-40 nm) in CH2Cl2 compared to the corresponding MTPPs. β-Dicyanovinyl substituted porphyrins were developed as a quantitatively operating 'lab-on-a-molecule' for the visual detection of F- and CN- ions. Having a CN- ion responsive dicyanovinyl moiety and a F- ion responsive redox-active 3,5-di-tert-butyl-4-hydroxyphenyl groups, they detect F- and CN- ions simultaneously by switching unique structural changes between porphyrin, porphodimethene and porphyrinogen along with distinct colour changes which were monitored by UV-Vis-NIR, fluorescence and NMR spectroscopic techniques.

We have synthesized 2,3,7,8,12,13,17,18-octachloro-meso-tetraphenylporphyrinatooxidovanadium(iv) (VOTPPCl8) and characterized by various spectroscopic (UV-Vis, IR and EPR) techniques, MALDI-TOF mass spectrometry and elemental analysis. The DFT optimized structure of VOTPPCl8 in CH3CN exhibited a highly nonplanar saddle shape conformation of the porphyrin macrocycle. The cyclic voltammogram of VOTPPCl8 showed a 500 mV anodic shift in the first ring reduction potential and 220 mV in the first ring oxidation potential compared to VOTPP indicating the electron deficient nature of the porphyrin π-system and further proving the existence of a nonplanar conformation of the macrocycle in solution. Further, VOTPPCl8 exhibited very high thermal stability till 390 °C as indicated in its thermogram. The oxidation state of the metal ion (V(IV)) was confirmed by EPR spectroscopy and VOTPPCl8 exhibited an axial spectrum which corresponds to the axially compressed dxy(1) configuration. VOTPPCl8 was utilised for the selective epoxidation of various olefins in good yields with very high TOF numbers (6566-9650 h(-1)) in the presence of H2O2 as an oxidant and NaHCO3 as a promoter in a CH3CN/H2O mixture. The oxidoperoxidovanadium(v) species is expected to be the intermediate during the catalytic reaction which is probed by (51)V NMR spectroscopy and MALDI-TOF mass analysis. Notably, VOTPPCl8 is stable after the catalytic reaction and doesn't form a μ-oxo dimer due to the highly electron deficient nonplanar porphyrin core and can be reused for several cycles.

Supramolecular integration of a saddle-distorted zinc(II) porphyrin complex, which has hydroxyl groups at the para-position of the four meso-aryl groups, has been demonstrated on the basis of hydrogen bonding among the peripheral hydroxyl groups. The hydrogen-bonding patterns were controlled by the recrystallization solvents and additives, and particularly, addition of a bifunctional ligand such as 4,4'-bipyridine (bpy). The coordination of bpy to form dinuclear Zn(II)-porphyrin complexes causes a conformational difference: the dimeric complex with four hydroxyl groups is in an eclipsed form, however, a derivative without hydroxyl groups is in a staggered form due to the presence or absence of the intermolecular hydrogen bonding. In addition, the dimerization by the bpy coordination resulted in the expansion of the intermolecular space formed in the porphyrin networks, suggesting the potential to be applied for inclusion of guest molecules.