Publications by authors named "Karolina Hurej"

A family of transition metal complexes of meso-aryl-2-aza-21-carbaporphyrin (N-confused porphyrin, NCP) derivatives acting as ortho-metallating ligands for ruthenium(II), rhodium(III), and iridium(III) is synthesized and characterized by XRD, spectroscopic, and electrochemical methods. The chirality of these systems is shown by the separation of the enantiomers and analyzed by circular dichroism and DFT. A preliminary catalytic study indicates the activity of the iridium(III) ortho-metallated complexes in the N-heterocyclization of primary amines with diols.

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The insertion of palladium(II) into di-p-pyrirubyrin results in mutually convertible bimetallic complexes. Post-synthetic functionalization of one of them yielded bispalladium(II) dioxo-di-p-pyrirubyrin and, after demetallation, dioxo-di-p-pyrirubyrin, introducing for the first time the α,β'-pyridin-2-one unit into the macrocyclic frame. Bispalladium(II) di-p-pyrirubyrin 6, bispalladium(II) dioxo-di-p-pyrirubyrin 9, and dioxo-di-p-pyrirubyrin 10 absorb and emit light around 1000 nm and are characterized by high photostability.

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The world of modified porphyrins changed forever when an N-confused porphyrin (NCP), a porphyrin isomer, was first published in 1994. The replacement of one inner nitrogen with a carbon atom revolutionised the chemistry that one is able to perform within the coordination cavity. One could explore new pathways in the organometallic chemistry of porphyrins by forcing a carbon fragment from the ring or an inner substituent to sit close to an inserted metal ion.

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The first, direct way from arylalkanes to 1,4-dicarbonyl compounds has been shown. It makes obtaining these useful products more accessible and cheaper. Our method is based on a one-pot reaction with excellent regioselectivity, mild conditions, and water as the main solvent.

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The formation of a precisely designed environment predefined for stabilizing electron-deficient atoms, such as boron(III), is an important approach for optimizing the properties of a chromophore. A triphyrin(2.1.

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The structurally prearranged carbaporphyrins 22-methyl- and 22-ethyl-m-benziporphyrins provide the platform stabilizing aromatic rhodium(III) 22-(μ-methylene-m-benziporphyrin) and rhodium(III) 22-(μ-ethylidene-m-benziporphyrin). An intramolecular conversion facilitated by the m-phenylene reactivity and observed for both aromatic complexes efficiently leads to rhodium(III) 21-(μ-methylene)-21-carbaporphyrin and rhodium(III) 21-(μ-ethylidene)-21-carbaporphyrin. The distinctive macrocyclic environment of rhodium(III) 21-carbaporphyrin created an opportunity to trap unique organometallic transformations of inner core substituents affording the fulvene-like bond pattern or the rearrangement to 21-vinyl substituent.

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A structurally prearranged carbaporphyrin, 22-methyl-m-benziporphyrin, provided the perfect macrocyclic platform to form gold(III) 22-methyl-m-benziporphyrin, which facilitates the specific m-benzene ring contraction yielding gold(III) 21-methyl 21-carbaporphyrin with remarkably high yield.

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A meso-N-pyrrole porphyrin converts into a π-extended porphyrin forming an indolizine-3-one motif. The indolizine-3-one frame opens a lactam subunit preserving a six-membered, heterocyclic structure fused with the main macrocycle. The optical properties of formed derivatives follow the structural modifications giving the absorbance and emission eventually modulated by the NH-centered modifications of the fused unit.

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The contraction of benzene is one of an exclusive group of reactions where the cleavage of aromatic structure is of fundamental importance. Rhodium(III) m-benziporphyrin undergoes an unprecedented transformation of the built-in m-phenylene in which a perimeter carbon atom is extruded to form rhodium(III) 21-carbaporphyrin, stabilizing the formyl-unit-substituted rhodacyclopropane motif.

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An aryl amine attached to the meso position of a porphyrin controls the π-delocalization using a redox process or a protonation/deprotonation centered at the meso-nitrogen. An easily accessible modulated motif affords a switchable near-IR chromophore as reflected by significant changes in absorption and fluorescence spectra.

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Triangularly shaped, contracted porphyrinoids belong to a group of molecules where the geometry significantly modifies the observed electronic properties. The need for a controllable, effective, and widely applicable approach to triphyrins drives extensive research towards macrocyclic materials that act as potential controlling motifs by switching their aromaticity. Two isomeric thiophene-fused triphyrins(2.

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