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A one-step, gram-scale protocol for the preparation of 1-imino-3-thioisoindolines and a novel one-pot two-step methodology of the synthesis of dithio- or diamino-β-isoindigo derivatives starting from phthalonitriles and sodium hydrosulfide in an aprotic dipolar solvent have been developed. It was demonstrated that the electronic properties of the substituent(s) in the phthalonitrile core play a critical role in β-isoindigo synthesis resulting either in the selective formation of dithio- or diamino-β-isoindigo chromophores. The

The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of "Manitoba dipyrromethenes" (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λ

The electronic communication between two ferrocene groups in the electron-deficient expanded aza-BODIPY analogue of zinc manitoba-dipyrromethene (MB-DIPY) was probed by spectroscopic, electrochemical, spectroelectrochemical, and theoretical methods. The excited-state dynamics involved sub-ps formation of the charge-separated state in the organometallic zinc MB-DIPYs, followed by recovery of the ground state via charge recombination in 12 ps. The excited-state behavior was contrasted with that observed in the parent complex that lacked the ferrocene electron donors and has a much longer excited-state lifetime (670 ps for the singlet state). Much longer decay times observed for the parent complex without ferrocene confirm that the main quenching mechanism in the ferrocene-containing 4 is reflective of the ultrafast ferrocene-to-MB-DIPY core charge transfer (CT).

This mini-review summarizes the synthesis strategies for the preparation and post-functionalization of aza-BODIPYs, BOPHYs, “half-Pcs”, biliazines, MB-DIPYs, semihemiporphyrazines, BOIMPYs, BOPPYs, BOPYPYs, BOAHYs, and BOAPYs.

The reaction between MB-DIPY sodium salts and Ag(I) ions results in the formation of unprecedented MB-DIPY2Ag2 dimers in both solution and the solid state. These dimers have a short Ag–Ag contact (∼2.9 A) and orthogonal twist in each of the MB-DIPY chromophores. The electronic structure of the unique dimers was probed by spectroscopic and theoretical methods.

We have developed a new synthetic strategy for the preparation of a series of isoindolin-1-imines and isoindolin-1-ones from aromatic ketones and phthalonitrile. Self-condensation reactions of these isoindolin-1-imines led to the formation of a novel class of benzo-fused, highly electron-deficient core-extended azadipyrromethene chromophores ("MB-DIPY"). The influence of temperature, catalyst, and the template ions on the self-condensation reaction rate, yield, and stereoselectivity was examined in detail. New chromophores (sodium, zinc, and metal-free compounds) were characterized by NMR, UV-vis, fluorescence, high-resolution mass spectroscopies, and in many cases, X-ray crystallography. Their redox properties were probed by electrochemical and spectroelectrochemical approaches that revealed the remarkable electron-accepting nature of the new systems. Stepwise one- and two-electron reduction of the new MB-DIPYs and their zinc complexes was investigated by spectroscopic and spectroelectrochemical methods. Both one- and two-electron reduced forms of all zinc complexes studied have strong absorption in the near-infrared region up to ∼1200 nm. Unusual spectroscopic and electrochemical properties of these dyes were correlated with their electronic structures and excited-state natures predicted by density functional theory (DFT) and time-dependent DFT calculations. Despite some structural similarities with well-known aza-BODIPYs, the new MB-DIPYs differ remarkably from them in spectroscopic and redox properties.

Complexation of methyl-glycine-amide functionalized thiacalix[4]arene with K(+) and Ag(+) has been studied using density functional theory (DFT) in the gas phase. To account for the conformational possibilities of the ligand, the free ligand and its potassium complexes were subjected to global minima searches on the molecular mechanics (MM) level of theory with the OPLS (optimized potentials for liquid simulations) force field. For the free ligand, the order of the energies and geometries of the ligand conformers is in agreement between MM and DFT; however, the position of K(+) in the ligand's cavity was predicted differently by these methods. Hydrogen bonding of amide hydrogens in the ligands' podand arms was found to take place predominantly with the ether oxygens of the same arm rather than the other arms' carbonyls. According to DFT calculations, the silver cation preferred to coordinate with one sulfur bridge and three carbonyl groups, whereas potassium cation favored interaction with the four carbonyl oxygens of the podand amide arms. Neither cation preferred the N-mode of coordination. For all obtained conformers, intramolecular hydrogen bonds disfavor complexation, increasing the preorganizational energy to be paid.