Michal Jacek Bialek

University of Wroclaw | WROC · Faculty of Chemistry

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 th...

The oxidation of 10,15‐diaryl‐21‐carba‐23‐selenaporphyrinoids resulted in the creation of dyads. The dimerization process follows the [5+2] cycloaddition path with the formation of an azepine unit. These arrays have two direct bonds between the peripheral carbocyclic carbon atoms of one carbaselenaporphyrinic subunit and the central carbon and nitr...

The architecture of self-assembled host molecules can profoundly affect the properties of the encapsulated guests. For example, a rigid cage with small windows can efficiently protect its contents from the environment; in contrast, tube-shaped, flexible hosts with large openings and an easily accessible cavity are ideally suited for catalysis. Here...

The oxidation of 10,15‐diaryl‐21‐carba‐23‐selenaporphyrinoids resulted in the creation of dyads. The dimerization process follows the [5+2] cycloaddition path with the formation of an azepine unit. These arrays have two direct bonds between the peripheral carbocyclic carbon atoms of one carbaselenaporphyrinic subunit and the central carbon and nitr...

Photoisomerization of azobenzenes from their stable E isomer to the metastable Z state is the basis of numerous applications of these molecules. However, this reaction typically requires ultraviolet light, which limits applicability. In this study, we introduce disequilibration by sensitization under confinement (DESC), a supramolecular approach to...

Incorporation of α,β'-pyridine moiety into expanded porphyrins opens a highly interesting area of research due to created the molecules' attractive optical and coordination properties. The insertion of palladium(II) into di-p-pyrirubyrin, results in mutually convertible bimetallic complexes. Post-synthetic functionalization of one of them yielded b...

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. Bisp...

The process of vision begins with the absorption of light by retinal, which triggers isomerization around a double bond and, consequently, a large conformational change in the surrounding protein opsin. However, certain organisms evolved different visual systems; for example, deep-sea fishes employ chlorophyll-like antennas capable of capturing red...

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 porp...

The peripheral functionalization of 10-azacorroles has been almost unexplored compared to the flourishing development of the functionalization of corroles. Here we explored the functionalization of 10-azacorroles through the study of...

Correction for ‘Functionalization of 10-azacorroles: nitration, bromination and acylation’ by Sha Li et al. , Org. Chem. Front. , 2023, https://doi.org/10.1039/d3qo00805c.

Molecular confinement effects can profoundly alter the physicochemical properties of the confined species. A plethora of organic molecules were encapsulated within the cavities of supramolecular hosts, and the impact of the cavity size and polarity was widely investigated. However, the extent to which the properties of the confined guests can be af...

Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately...

Confining molecules within well-defined nanosized spaces can profoundly alter their physicochemical characteristics. For example, the controlled aggregation of chromophores into discrete oligomers has been shown to tune their optical properties whereas encapsulation of reactive species within molecular hosts can increase their stability. The resazu...

The unique [Fe(CO) 5 ]-induced cyclocarbonylation of the phenanthriporphyrin's core is an intriguing example of a post-synthetic core modification of the macrocycle. The reaction involves the activation of C(22)−H and C(25)−H bonds,...

A rational synthesis using carba analogues of tripyrrane and 1,3-bis(arylhydroxymethyl)furan as synthons resulted in the formation of 21-carba-23-oxaporphyrin and 21-carba-23-oxachlorin.The molecular design preserves all essential virtues of 21-oxaporphyrin architecture allowing...

Invited for the cover of this issue is Lechosław Latos‐Grażyński and co‐workers at University of Wrocław. The image depicts two essential conformations of 31,34‐dicarba[26]hexachlorins: dumbbell and rectangular with regular or doubly inverted carbocyclic rings, respectively. Read the full text of the article at 10.1002/chem.202002603. “The incorpor...

“Jumpy” five‐membered carbocycles in carbaporphyrinoids: Dicarba[26]hexachlorins(1.1.1.1.1.1.) with built‐in cyclopentenyl and cyclopentadienyl moieties can adopt two essential conformations: dumbbell‐shaped and rectangular convoluted respectively with regular and doubly inverted carbocyclic rings. The transformation between conformers has been con...

Incorporation of cyclopentene fragments into a skeleton of parental [26]hexaphyrin(1.1.1.1.1.1) afforded extended carbaporphyrinoids: 31,34‐dicarbahexa[26]chlorin and its derivatives: the first externally substituted by ethoxy and 2,4,6‐trimethylbenzylidene groups and the second one formed by selective oxidation of one cyclopentene ring. Macrocycle...

The carbaporphyrinoid rollercoaster: Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0) exists as two locked figure‐eight isomers that demonstrate multiple conformational rearrangements and anion‐binding events upon protonation. Formation of one of the final dications is accompanied by an inclusion of a complex anion within the cavity yielding a pseudorotaxan...

The facile method of the exocyclic π-extension of the carbaporphyrinoid embedding phenanthrene moiety – phenanthriporphyrin – has been described. The reaction between 5,6-dioxophenanthriporphyrin and a series of aliphatic and aromatic amines provided a family of carbaporphyrinoids incorporating azaacene components. The 1H NMR spectrocopic, electroc...

Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0), an expanded carbaporphyrinoid incorporating two phenanthrenylene moieties, exists as two separate, yet interconvertible, locked stereoisomers. These species demonstrate complex dynamic behavior upon protonation, consisting of multiple conformational rearrangements and anion‐binding events. Formation of one o...

Arylazopyrazoles represent a new family of molecular photoswitches characterized by a near-quantitative conversion between two states and long thermal half-lives of the metastable state. Here, we investigated the behavior of a model arylazopyrazole in the presence of a self-assembled cage based on Pd–imidazole coordination. Owing to its high water...

Invited for the cover of this issue is Lechosław Latos‐Grażyński and co‐workers at University of Wrocław. The image depicts cobalt(II) azuliporphyrin as a magical organometallic platform to perform other types of chemistry, that is, dioxygen activation, aromaticity control, and construction of intermetallic communication motifs. Read the full text...

An organometallic platform, azuliporphyrin, was used to explore CoII and CuII reactivity. The activation of C(sp2)–H occurs with formation of a C−MII bond. The metal center activates a dioxygen molecule that enables the oxygen atom insertion into the organometallic bond. During the formation of the diamagnetic cobalt complexes, the macrocycle aroma...

Diamondoid nanoporous crystals represent a synthetically challenging class of materials that typically have been obtained from tetrahedral building blocks. In this issue of Chem, Stoddart and coworkers demonstrate that it is possible to generate diamondoid frameworks from a hexacationic building block lacking a tetrahedral symmetry. These results h...

Photooxidation of copper(III) 5,6-dimethoxyphenathriporphyrin and copper(III) 5,6-dioxophenanthriporphyrin, which contain phenanthrene or dioxophenathrene moieties built into the macrocyclic frameworks, resulted in the regioselective cleavage that afforded organometallic copper(III) complexes of open-chain phenanthribilinone-type acyclic ligands te...

Taking advantage of specific properties of azuliporphyrin and reactivity of cobalt(II), activation of azulene C(sp²)–H occurred and organometallic complexes with Co–C bonding were formed. The system allowed for macrocyclic aromaticity tuning through metal coordination and oxidation. Due to Co(II)–C and parallel tested Cu(II)–C reactivity and the af...

5,6-Dimethoxyphenanthriporphyrin 1 and 5,6-dioxophenanthriporphyrin 2 act as suitable organometallic ligands for copper(III), adopting trianionic [CCNN] coordination cores. Under oxidizing conditions, in the presence of methanol, copper(III) phenanthriporphyrin 1-Cu undergoes transformation to copper(III) phenanthriporphodimethene with methoxy subs...

Diazuli‐p‐benzithiaporphyrinogens and their oxidized polycarbocationic forms provide intriguing examples of azuliporphyrinoids that incorporate the p‐phenylene unit into the macrocyclic framework of expanded porphyrinoid. In their manuscript, L. Latos‐Grażyński and co‐workers also demonstrated that these hybrid macrocycles can acquire a role of a c...

The incorporation of a 9,10-dimethoxyphenanthrene moiety into a porphyrin framework results in the formation of a hybrid macrocycle – 5,6-dimethoxyphenanthriporphyrin 1, fusing the structural features of polycyclic aromatic hydrocarbons and porphyrins. Simple transformations of antiaromatic 1 led to two macrocycles incorporating phenanthrene and ph...

A porphyrinogen macrocycle incorporating two azulenes, phenylene and thiophene into the framework, joined by four C(sp3) atoms has been obtained as a mixture of six isomers. They were successfully separated and characterized spectroscopically. The identity of two of them was confirmed by X‐ray crystallography. One isomer was tested in reaction with...

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S‐shaped aza[5]helicene. Criss‐cross: Incorporation of a phenanthrene moiety into a he...

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S‐shaped aza[5]helicene. Kreuzweise Einführung einer Phenanthreneinheit in einen Hexap...

The incorporation of an azulene bridge into an aromatic hexaphyrin framework allows to manipulate [small pi]-electron delocalization pathways. The palladium(II) complex undergoes the hydroxyl-triggered azulene contraction or isomerization to an oxynaphthalene unit transforming the hexaphyrin framework into meso-linked carbaporphyrins. This converts...

The reaction of [Ru3(CO)12] with a series of conformationally flexible thiaazuliporphyrinogens, namely, dithiadiazuli-, thiatriazuli- and tetraazuliporphyrinogen, yielded a series of complexes with two azulene rings coordinated by either Ru2(CO)5 and Ru4(CO)9 or two Ru4(CO)9 clusters. For dithiadiazuliporphyrinogen, three fundamental arrangements w...

This review underscores the conformational flexibility of porphyrinoids, a unique class of functional molecules, starting from the smallest triphyrins(1.1.1) via [18]porphyrin(1.1.1.1) to conclude with a variety of expanded porphyrinoids and heteroporphyrinoids including enormous [96]tetracosaphyrin(1.0.1.0.1.0.1.0.1.0.1.0.1.0.1.0.1.0.1.0.1.0.1.0)....

In the search of porphyrin arrays with a unique geometry, the efficient synthesis of a directly linked 21-carba-23-thiaporphyrin dimer with the distinctive dihydrofulvalene bridging motif has been developed. This compound acquires an uncommon parallel-displaced arrangement of two carbaporphyrin planes. The dimer undergoes an acid-triggered cleavage...

In the search of porphyrin arrays with a unique geometry, the efficient synthesis of a directly linked 21-carba-23-thiaporphyrin dimer with the distinctive dihydrofulvalene bridging motif has been developed. This compound acquires an uncommon parallel-displaced arrangement of two carbaporphyrin planes. The dimer undergoes an acid-triggered cleavage...

32-Hetero-5,6-dimethoxyphenanthrisapphyrins-macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins-were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5-bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π-electr...

In the search for tricarbaporphyrinoids, a threecomponent acid-catalyzed condensation of azulene, 2,5- bis[(p-tolyl)hydroxymethyl]thiophene, and an aryl aldehyde has been elaborated, affording the appropriate thiatriazuliporphyrinogens. The subsequent oxidation yielded a rare example of a macrocyclic organic tetracation, which can be readily and re...

5,10,15,20-Tetraaryl-23-thiaazuliporphyrin (SAz) was synthesized starting from non-functionalized azulene using an "1+3" method to be applied as a monoanionic macrocyclic ligand which provides a peculiar [CNSN] coordination cavity. An insertion of palladium(II) afforded the cationic [PdII(SAz)]+, which readily undergoes the 7-membered ring contract...

Powder second-harmonic generation (SHG) efficiencies are usually measured at single wavelengths. In the present work, we provide a proof of concept of spectrally resolved powder SHG measured for a newly obtained series of three non-centrosymmetric coordination polymers (CPs). CPs are constructed from tetrahedral linker-tetraphenylmethane-based tetr...

Powder second-harmonic generation (SHG) efficiencies are usually measured at single wavelengths. In the present work, we provide a proof of concept of spectrally resolved powder SHG measured for a newly obtained series of three non-centrosymmetric coordination polymers (CPs). CPs are constructed from tetrahedral linker–tetraphenylmethane-based tetr...

Chemical oxidation and oxygenation of carbonyl ruthenium(II) azuliporphyrin [Ru(TPAP)(CO)] were explored. [Ru(TPAP)(CO)] reacts with dioxygen giving carbonyl ruthenium(II) 21-oxyazuliporphyrin [Ru(TPAP-O)(CO)] revealing the activation the Ru-C bond inside azuliporphyrin coordination cavity. Solution and X-ray structural studies confirmed the tenden...

The insertion of ruthenium(II) into azuliporphyrin (TPAP) has yielded carbonyl ruthenium(II) azuliporphyrin [Ru(TPAP)(CO)] featuring an equatorial CNNN set of donors. Its azulene moiety serves as the π-coordination platform to accommodate the Ru4(CO)9 cluster. This chemistry proved to be general giving rise to a series of bimetallic complexes [M(TP...

Naphthalene-1,5-diphosphonic acid [C10H6(PO3H2)2, H4NDP(1,5), 1] and its more flexible counterpart, naphthalene-1,5-bis(methylphosphonic) acid [C10H6(CH2PO3H2)2, H4NDP(1C,5C), 2], have been synthesized, characterized, and used as building blocks in supramolecular assemblies with 4-(N,N-dimethylamino)pyridine (DMAP) and morpholine. The two acids gen...

Two diphosphonic acids based on naphthalene scaffold, namely naphthalene-1,4-diphosphonic acid, C10H6(PO3H2)2 [1, H4NDP(1,4)] and 1-(phosphono)naphthalene-4-(methylphosphonic) acid, C10H6(PO3H2)(CH2PO3H2) [2, H4NDP(1,4C)] were obtained. Their supramolecular self-assembly were studied as well as solvent effect for the second one (2a, 2b). These pote...

The scope of this chapter is to describe selected methods of synthesis of phosphonic acids and their esters which have found use in metal phosphonates chemistry. In the first place some physicochemical properties of phosphonic group are mentioned. Those are geometry, acidity and coordination of phosphonic group compared to other groups commonly use...