Pradeepta K. Panda

Dinaphthoporphycenes: synthesis and nonlinear optical studies.

Naphthobipyrrole-derived porphycenes are synthesized for the first time via McMurry coupling of the β-alkylated 2,9-diformylnaphthobipyrrole derivatives, which in turn were prepared easily from 2,3-naphthalene bishydrazine in four steps. Insertion of nickel into the porphycene core results in transformation of the rectangular N4-core into a square type geometry owing to the fusion of naphthalene moiety onto the bipyrrole entities. These porphycenes show large, intensity dependent three-photon absorption.

Colorimetric sensing of fluoride ion by new expanded calix[4]pyrrole through anion-π interaction.

Three new expanded calix[4]pyrroles were synthesized, where the two dialkylldipyrromethane units are linked via C-C double bonds. One of them, calix[2]bispyrrolylethene, colorimetrically senses fluoride ion only, owing to anion-π interaction in polar aprotic solvents.

Ultrafast excited state dynamics and dispersion studies of nonlinear optical properties in dinaphthoporphycenes

Ultrafast excited state dynamics of dinaphthoporphycenes were investigated using femtosecond and picosecond degenerate pump-probe techniques at 600 nm and 800 nm, respectively. Femtosecond pump-probe data indicated photo-induced absorption at 600 nm resulting from two-photon/single photon excitation, whereas picosecond pump-probe data demonstrated photo-bleaching which was a consequence of three-photon absorption. The fastest lifetimes (100–120 fs) observed are attributed to the intramolecular vibrational relaxation, the slower ones (1–3 ps) to internal conversion, and the slowest components (7–10 ps) to non-radiative decay back to ground state. Z-scan studies in the 560–600 nm range were also carried out.

Fluorescent turn-off based sensing of nitrated explosives using porphyrins and their Zn(II)-derivatives

A series of porphyrins and their corresponding Zn(II)-derivatives possessing both electron donating and electron withdrawing substituents at their periphery, have been investigated for the detection of nitrated explosives, which includes nitroaromatics, plastic explosive taggant (DMNB) and explosive nitramines (RDX and HMX), using a fluorescence turn-off mechanism. Among them, β-octamethoxyporphyrin displays the maximum response towards TNT with a KSV of 324 M−1.

Conformational and spectroscopic properties of π-extended, bipyrrole-fused rubyrin and sapphyrin derivatives.

Two new expanded porphyrins, naphthorubyrin and naphthosapphyrin, were synthesized. The π-extended rubyrin was isolated and structurally characterized in its monoprotonated form. The sapphyrin congener undergoes pyrrole inversion as a function of the protonation state. These conformational effects are reflected in the spectroscopic features, including the excited singlet state lifetimes.

Annulated Isomeric, Expanded, and Contracted Porphyrins

Compared to porphyrin, its isomeric, expanded, and contracted analogues are less well explored. This contrast is found to be even more drastic in the case of their peripherally annulated counterparts. Nevertheless, the chemistry of annulated isomeric, expanded, and contracted porphyrins started flourishing recently with considerable efforts over the past few years, as evidenced by an increasing number of publications. While keeping the essence of porphyrins, these annulated versions exhibit quite unique properties that have no precedence in their nonannulated counterparts. An in-depth update of research carried out so far in this emerging area will be presented in this review.

Structure, electronic states, and anion-binding properties of cyclo[4]naphthobipyrroles.

Three octaalkyl-substituted cyclo[4]naphthobipyrroles, studied in solution in the form of their sulfates, reveal absorption and magnetic circular dichroism (MCD) spectra very similar to those of the parent cyclo[8]pyrrole. A unique feature of these systems is a strong absorption in the near IR region. The analysis of MCD patterns based on a perimeter model reveals a hard-chromophore character of cyclo[4]naphthobipyrroles, i.e., ΔHOMO ≪ ΔLUMO. Comparison of Raman spectra obtained for crystalline samples and solutions, combined with the analysis of absorption and MCD spectra based on quantum chemical calculations reveals that cyclo[4]naphthobipyrroles exist in solutions as undissociated sulfates of the doubly protonated forms.

Naphthobipyrrole-derived sapphyrins: rational synthesis, characterization, nonlinear optical properties, and excited-state dynamics.

Two new free-base β-octa and hexaalkyl naphthobipyrrole-derived sapphyrins are reported along with various salts thereof. One of them has substituents at all of its β positions, whereas the pyrrole unit opposite to the bipyrrolic moiety is unsubstituted in the other. The effect of bipyrrole fusion on the structure of sapphyrins was explored. Interestingly, an unprecedented sandwiched supramolecular aqua-bridged free-base sapphyrin dimer was also characterized in the solid state. Further, the effect of anions on the third-order nonlinear optical properties of these sapphyrins were explored in the salt form, along with their detailed excited-state dynamics by both degenerate and nondegenerate pump-probe studies.

β-Octamethoxy-Substituted 22π and 26π Stretched Porphycenes: Synthesis, Characterization, Photodynamics, and Nonlinear Optical Studies

Three meso-expanded tetrapyrrolic aromatic macrocycles, including 22π and 26π acetylene-cumulene bridged stretched octamethoxyporphycenes and octamethoxy[22]porphyrin-(2.2.2.2), are reported, for the first time, by modification of previously reported synthetic methods. This strategy led to an enhancement in the overall yield of their corresponding octaethyl analogues. The methoxy-substituted expanded porphycenes display slightly blueshifted absorption relative to their ethyl analogues, along with very weak fluorescence, probably due to efficient intramolecular charge transfer (ICT). Additionally, the two-photon absorption (TPA) cross sections of these macrocycles were evaluated; these are strongly related to core expansion of the porphyrin aromaticity through increased meso-bridging carbon atoms as well as conformational flexibility and substitution effects at the macrocyclic periphery. In particular, the octamethoxy stretched porphycenes display strong TPA compared with the octaethyl analogues due to the dominant ICT character of methoxy groups with a maximum TPA cross section of 830 GM at 1700 nm observed for 26π-octamethoxyacetylene-cumuleneporphycene.

β,β′-Bipyrrole Fusion-Driven cis-Bimetallic Complexation in Isomeric Porphyrin

An unprecedented cis-bimetallic complex of dinaphthoporphycene (DNP), namely [Pd2(μ-DNP)(μ-OAc)2], is reported. The most striking feature of this complex is that two palladiums coordinate to the macrocycle on the same side and are closely held together (Pd-Pd: 2.67 Å) by two bridging acetate ligands exhibiting significant metal-metal bonding interaction (bond order 0.18 evaluated by NBO analysis). Interestingly, replacing acetate with acetylacetonate (acac) could stabilize an unusual mono-palladium complex of DNP, where Pd coordinates unsymmetrically to two ring Ns above the macrocyclic plane, as well as coordinating with two Os of the acac ligand. Remarkably, the rigid DNP core displays enhanced complexation induced aromaticity (as per NICS and HOMA analysis), despite undergoing severe core deformation during complexation with metal ion(s) as noticed from their solid-state structures.