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Recent advances in the chemistry of main group porphyrin complexes are surveyed. New, unprecedented structural types for porphyrin complexes which have been revealed from the recent reports of boron and tellurium porphyrins are described. Advances in the preparation and reactivity of Group 14 (silicon and tin) and Group 15 porphyrin complexes are discussed. A systematic variation in the out-of-plane distortion (ruffling) of light element Group 14 and 15 porphyrin complexes has become apparent now that a significant number of structurally characterized examples are at hand.

As ²¹³Bi, a spontaneous alpha-emitting radioisotope, and ¹⁰B, a neutron-activated source of alpha particles, have been found to be potential tools in the treatment of cancer patients, a novel bismuth porphyrin, bearing both boron atoms and a strap with a hanging carboxylic group, was synthesized.

Organometallic porphyrins with a metal, metalloid or phosphorus fragment directly attached to their carbon framework emerged for the first time in 1976, and these macrocycles have been intensively investigated in the past decade. The present review summarises for the first time all reported examples as well as applications of these systems.

In this paper, we describe some observations from the attempted reaction of Br-BsubPc with phenol in DMF and DMAc. During these efforts, we found that Br-BsubPc reacts with the respective solvents to produce axially substituted formate-BsubPc and acetate-BsubPc. When no phenol is present the reaction proceeds to completion in a relatively short period of time. However, when phenol was present in DMF the reaction produced a mixture of formate-BsubPc, phenoxy-BsubPc, and HO-BsubPc. Similar results were found for the less-reactive Cl-BsubPc and MsO-BsubPc. Aside from these observations, it was found that simple heating in wet acetone of Br-BsubPc quantitatively produced HO-BsubPc after a facile workup. This method of producing HO-BsubPc removes the high temperatures, long reaction times, and harmful chemicals required in other synthetic methods. These results are relevant to anyone considering the reaction of BsubPcs in polar aprotic solvents.

Unprecedentedly large subporphyrazines (SubPz) with dibenzoquinoxalino-fusion and peripheral phenyl substitution were prepared by the cyclization of perfluorated or non-fluorous polyphenyl-substituted quinoxaline dinitriles and characterized by spectroscopic techniques. The compounds suitability to act as photosensitizers was explored by wavelength-specific induction of singlet oxygen luminescence and was shown to be excellent. Determination of ¹O₂-quantum yields suggests that fluorine substitution enhances the photosensitization efficiencies of the SubPz. On the other hand, cyclic voltammetry reveals an increase of irreversible reductive processes in case of the fluorinated SubPz.

In this study, the monomeric subphthalocyanines bearing azido (2) and terminal ethynyl (3) groups were synthesized. These subphthalocyanines were converted to their dimeric derivatives using azide-alkyne Huisgen cycloaddition and palladium-catalyzed Glaser–Hay coupling reactions subphthalocyanine (4) and (5), respectively. The novel subphthalocyanines were fully characterized by elemental analysis and general spectroscopic methods such as MALDI-TOF mass, FT-IR, UV-vis and ${}^{\mathrm{\text{1}}}$H-NMR. All synthesized subphthalocyanines showed quite good solubility in the most of common organic solvents. The fluorescence measurements were conducted for these subphthalocyanines to estimate their fluorescence quantum yields. The singlet oxygen generation abilities were also examined to investigate their photosensitizer properties.

The goal of this study was to develop mixtures of peripherally halogenated boron subphthalocyanines (BsubPcs) to explore these macrocycles as mixed alloys for applications within the organic electronic space. These halogenated BsubPc mixtures were synthesized by reacting mixtures of commercially available phthalonitriles, namely 4,5-dichlorophthalonitrile (Cl₂-pn), 4,5-difluorophthalonitrile (F₂-pn), tetrachlorophthalonitrile (Cl₄-pn), and tetrafluorophthalonitrile (F₄-pn), with boron trichloride (BCl${}_3)$ to achieve mixed halogenation upon formation of the BsubPcs. More specifically, as named, Cl₂-pn + F₂-pn and Cl₄-pn + F₄-pn mixtures were used to form Cl-Cl${}_{2\mathrm{\text{n}}}$F${}_{2\mathrm{\text{m}}}$BsubPc and Cl-Cl${}_{4\mathrm{\text{n}}}$F${}_{4\mathrm{\text{m}}}$BsubPc, respectively. To establish a firm synthetic methodology, the reaction kinetics of forming the BsubPc mixtures from their respective phthalonitrile mixtures were compared to the kinetics of the standard procedures forming the individual BsubPcs, for example, Cl-Cl${}_{12}$BsubPc from Cl₄-pn. As we use BCl₃ to form the BsubPcs, the axial bond is in general chloride, but we observed again random fluoride axial exchange, and therefore moved to the second step to have complete axial fluorination. Crude mixed halogenated BsubPcs were sublimed at high purities to enable physical characterization, including a study of UV-Vis absorption spectra differentiation, and cyclic (CV) and differential pulse voltammograms (DPV) electrochemical differentiation. We also did density functional theory (DFT) calculations for points of physical properties comparison. The comparison points are together with fully peripherally chlorinated Cl${}_{\mathrm{\text{n}}}$BsubPcs and fluorinated F${}_{\mathrm{\text{n}}}$BsubPcs. Given the outcomes, we foresee in future studies the ability to tune different ratios of peripherally halogenated BsubPc mixtures via synthetic tools, to enable tuning of the HOMO LUMO energy levels, which could consequently tune their application and performance in organic electronics.

Boron subphthalocyanines (BsubPcs) are versatile molecules with advantageous properties for applications. The BsubPcs are synthesized by the cyclotrimerization of a phthalonitrile and are composed of three isoindole subunits bound by three aza-/imine-bridging nitrogens. There are a variety of BsubPc derivatives shown within the literature due to the differentiation of a phthalonitrile precursor. The differentiation of a phthalonitrile enables the peripheral functional groups. The BsubPcs can be derivatized in two steps: First step is the cyclotrimerization of a phthalonitrile in the presence of a strong Lewis Acid, typically a boron trihalide (BX3) and enables a remaining axial substituent that is a B-X${}_a$ bond; second step is optional, the B-X${}_a$ bond can react with a nucleophile and results in B-X${}_b$. If the starting phthalonitrile is asymmetric, it will result in a combination of isomers. For this study, our approach is to have bromine substituents and to study their physical properties to see if applicable to organic electronic applications; chlorine and fluorine have been in past studies as halogens are unique and variations may present useful tools as they are known for electronegativities. The general phthalonitrile with no substitutions is produced in industry from $o$-xylene. There are a variety of ways to synthesize other phthalonitriles with halogens. However, phthalonitriles can also be made by a method that has the most versatility with its substituents and can start with phthalic acid and go to phthalic anhydride to phthalimide to phthalamide and final to phthalonitrile; it is also possible to synthesize a phthalimide directly from phthalic acid, and this is part of this study as we were focusing on bromination, we also wanted to optimize the synthetic pathways to brominated phthalonitriles, and we took an engineering perspective and for this study, we wish to show you.