Journal of Porphyrins and Phthalocyanines

Ligands bind reversibly to metal porphyrins in processes such as molecular recognition, electron transport and catalysis. These chemically relevant processes are ubiquitous in biology and are important in technological applications. In this article, we focus on the current advances in ligand binding to metal porphyrin receptors noncovalently bound at the solution/solid interface. In particular, we restrict ourselves to studies at the single molecule level. Dynamics of the binding/dissociation process can be monitored by scanning tunneling microscopy (STM) and can yield both qualitative and quantitative information about ligand binding affinity and the energetics that define a particular ligation reaction. Molecular and time dependent imaging can establish whether the process under study is at equilibrium. Ligand-concentration-dependent studies have been used to determine adsorption isotherms and thermodynamic data for processes occurring at the solution/solid interface. In several binding reactions, the solid support acted as an electron-donating fifth coordination site, thereby significantly changing the metal porphyrin receptor’s affinity for exogenous ligands. Supporting calculations provide insight into the metalloporphyrin/support and ligand–metalloporphyrin/support interactions and their energetics.

The dye molecules behaving as photosensitizers in dye-sensitized solar cells are the most critical factors to determine the power conversion efficiency. Therefore, ways to design dye molecules with excellent photoelectric properties has been the focus of dye-sensitized solar cells research. Here, we selected four representative different metal-corrole monomers to characterize their structures and photoelectronic properties. Then based on these metal-corrole monomers, six different architectures of metal-dicorroles were designed by varying the linking forms. The most stable architecture $a$ was screened out by binding energy calculations. A further two types of metal-dicorrole-based dyes were constructed by incorporating different bridge groups with the cyanoacry acceptor into the stable metal-dicorroles. A large number of density functional theory calculations and photoelectric properties analysis indicate that among these different metal-dicorrole-based dyes, Ga-dicorrole dyes have two strong and wide absorption bands in the visible region corresponding to Soret and Q bands, respectively, and have high charge separation efficiency under optical excitation. Especially for Ga-SN dye, by incorporating a $\pi$-bridge-conjugated group, its Soret absorption band is greatly enhanced, broadened and red-shifted, resulting in its merging with the Q band into one absorption band. Moreover, its charge transfer efficiency is up to 76.86%, which will facilitate its coupling with semiconductor materials and transfer its electrons to the semiconductor materials.

We report a series of alkyne-functionalized meso-aryl boron dipyrrin (BODIPY) molecular rotors sensitive to viscosity. The planar and twisted conformation within the molecular structure decides the viscosity-dependent behavior. The variations in fluorescence lifetime and intensity were appreciable to the local viscosity. Hence, the dye has been successfully employed in the enumeration of microbes by considering the proportionate fluorescence intensity of the BODIPYs as an index of the number of cells per mL. With increasing cells per mL, the viscosity of the bacterial solution is increased. Consequently, the fluorescence intensity of the sample containing BODIPY tends to increase due to the restricted rotation in the viscous medium. The BODIPY probe offers high sensitivity and is easier than other conventional techniques of colony-forming unit (CFU) determination. The theoretical studies indicate that intramolecular charge transfer is responsible for the enhanced fluorescence intensity in a highly viscous solvent.

We have systematically carried out a density functional theory-based investigation to understand the structural and electronic properties of various fused metalloporphyrin nanotubes (MPNT; M = Sc and Ti) by varying their diameters ranging from 7.91 Å to 18.70 Å for ScPNT and 7.90 Å to 18.59 Å for TiPNT. Binding energies and curvature energies are calculated to access the binding strength and stability of the nanotubes (NTs). From band structure and density of states, it is observed that the ScPNTs are metallic in nature and TiPNTs are semiconductors with small band gaps. The energy gap increases with increasing tube diameter. Our study also indicates that the transition metal atoms play an important role in determining the electrical nature (metallic or semiconducting) of the NTs. Furthermore, work functions for the fused NTs are found to decrease with increasing tube diameter. These results may have direct relevance to the technological applications in terms of band gap engineering or controlled thermionic emission.

In this study, we synthesized a new porphyrin-perinaphthothioindigo composite in which two porphyrins are connected to a perinaphthothioindigo dye through ethynyl linkages. The UV-vis absorption spectra of the composite showed an absorption peak originating from the trans-isomer at around 730 nm. Upon photoirradiation at 760 nm, the intensity of this absorption decreased with increasing absorption of the cis-isomer around 500 nm. The HOMO–LUMO absorption of the cis-isomer is blue-shifted by ˜230 nm compared to that of trans-isomer due to lack of $\pi$ conjugation. The shift by 230 nm is 100 nm larger than that observed for the monoporphyrin-substituted compound, indicating the expansion of $\pi$ conjugation by the additional porphyrin.

To enhance the nonlinear optical properties of graphene oxide in organic solvent and polymeric matrix, lutecium phthalocyanines (LuPc) and hyperbranched lutecium phthalocyanines (HBLuPc) have been grafted on the surface of graphene oxide, respectively. After the surficial modification, the electron transfer process between phthalocyanines and graphene oxide has been also facilitated, resulting in significant fluorescence quenching. Given the combination of nonlinear scattering, two-photon absorption with reverse saturable absorption and the photo-induced electron or energy transfer from the electron donor (phthalocyanine moiety) to the acceptor (graphene oxide), stronger nonlinear optical properties can be realized based on graphene oxide hybrids compared with graphene oxide and phthalocyanines. Furthermore, graphene oxide hybrid modified by hyperbranched lutecium phthalocyanines exhibits the best optical limiting response and the highest nonlinear extinction coefficient at 532 nm in both organic solvent and polymeric matrix. Interestingly, we also find that it could exhibit better optical limiting properties than those possessed by pure phthalocyanine at 1064 nm.

The preparation and assessment of carbonic anhydrase and paraoxonase enzyme inhibition properties of 3-(2-(5-amino-4-(4-bromophenyl)-3-methyl-1H-pyrazol-1-yl)ethoxy)phthalonitrile (2) and its nitrogen-containing non-peripheral phthalocyanine derivatives (3 and 4) are reported for the first time. The new phthalonitrile and its phthalocyanine derivatives have been elucidated by FT-IR spectroscopy, ¹H-NMR, ${}^{13}$C-NMR, mass and UV-vis spectroscopy. The results demonstrated that all synthesized compounds moderately inhibited carbonic anhydrase and paraoxonase enzymes. Among the compounds, the most active ones were found to be compound 4 for PON (Ki : 0.14 $\mu$M), compound 3 for hCA I (Ki : 22.52 $\mu$M) and compound 1 for hCA II (Ki : 13.62 $\mu$M).

Transition-metal-catalyzed homo and hetero coupling is a rapidly growing area of research. This work refers to the nickel-catalyzed photoinduced amination study of $\beta$-bromotetraarylporphyrin and its Ni(II), Zn(II) and Cu(II) complexes. The selective mono $\beta$-bromination of 5,10,15,20-tetrakis(4$\prime$-isopropylphenyl)porphyrin was achieved with $N$-bromosuccinimide. Under similar conditions, $\beta$-bromination of Ni(II), Zn(II) and Cu(II) complexes of 5,10,15,20-tetrakis(4$\prime$-isopropylphenyl)porphyrin successfully afforded the corresponding 2-bromometalloporphyrins. The $\beta$-bromoporphyrin/metalloporphyrins were coupled with three different amines through the creation of the C–N bond by using an economical and air-tolerant photoactive catalyst (NiBr${}_2^{}$ · 3H₂O) at room temperature under 365 nm radiations. Nickel-catalyzed amination yields are compared with the traditional Buchwald–Hartwig amination yields. Due to the low operational cost, photoinduced nickel-catalyzed C–N couplings were found to be more economical than the Buchwald–Hartwig amination procedure, although the latter afforded higher yields. The nickel-catalyzed photoamination reaction was also extended for the one-pot synthesis of pyridine-3,5-diamine bridged porphyrin dyad. The intramolecular cyclization of the pyridine-3,5-diamine-bridged porphyrin dyad afforded a novel quinolino-fused porphyrin dyad. Degree- and distance-based topological indices of the newly synthesized porphyrins were calculated and correlated with their molar refractivity. All newly synthesized porphyrins are characterized by UV-vis, FTIR, ¹H NMR, elemental analysis and mass spectrometry.

A rigid Zn–trisporphyrin (1), the Zinc complex of 2,4,6-tris(5,10,15-triphenylporphyrinatozinc)-1,3,5-triazine (2) with three porphyrin moieties bridged by a rigid 1,3,5-triazine group, was synthesized and characterized by a series of spectroscopic methods including mass, ¹H NMR, electronic absorption, and IR spectroscopy in addition to elemental analysis. The UV-vis spectrophotometric titration results revealed that along with the addition of the 1,4-diazabicyclo[2.2.2]octane (DABCO) form 0 to 3 equiv, 1 could form a 2:3 sandwich-type coordination cage in chloroform, which then transformed into a 1:3 open complex when the DABCO concentration was more than 3 equiv. Such DABCO-induced self- and disassembly processes were also confirmed by ¹H NMR spectrophotometric titrations. In particular, it was demonstrated by comparative studies that the synergistic effect of the three porphyrin moieties linked together by the rigid 1,3,5-triazine group in 1 promoted the formation and stabilization of the 2:3 sandwich-type coordination cage. This result will be helpful towards the fabrication of various self-assembly structures based on metalloporphyrins with application potential in diverse areas such as molecular recognition and separation.

Incorporating fluorine atoms into a molecule can endow it with various unique properties that enable materials applications. Selective solubility in fluorous solvents is achieved by a high fluorine content and selective partitioning into perfluorinated liquids over organic and aqueous phases provides orthogonal opportunities for chemistry and materials assembly. Although there is a growing number of partially fluorinated molecules, there are insufficient structural design principles to produce diverse fluorous soluble dyes. Herein, we report the synthesis of six fluorous phthalocyanine and subphthalocyanine dyes, and study their properties in the fluorous phase. Phthalocyanines generally display limited solubility and we also observed apparent aggregation in the fluorous phase. However, the nonplanar subphthalocyanines showed greater solubility. Subphthalocyanines also displayed fluorescence in selected solvents, and their emissive properties were investigated. The materials described expand the library of fluorous dyes and provide insights for the design of new molecules with fluorous solubility.