Heterobimetallic 21,23-dimetallaporphyrin: activation of metal-metal interactions within the porphyrinoid macrocycle.

Two core-modified porphyrins containing metal atoms, namely platinum(II) or platinum(IV) and rhodium(III), in place of two NH units, have been obtained by a post-synthetic modification of the 21,23-ditelluraporphyrin. The products of the tellurium-to-metal exchange, 21-platina-23-rhodaporphyrins, incorporate rhodacyclopentadiene and platinacyclopentadiene units with the metal atoms facing each other. The two molecules exhibit different degrees of metal-metal interaction depending on the oxidation state of platinum, with the NBO bond order being 0.04 for platinum(IV) and 0.15 for platinum(II). Consistently, the Quantum Theory of Atoms in Molecules analysis revealed the presence of the bond determinant, the bond critical point, in the platinum(II) species, in contrast to the platinum(IV) congener. The two porphyrinoids are interconvertible in redox reactions. They both exhibit fluxional behaviour in solution, studied by 1H NMR, involving alteration in the metal ion coordination sphere accompanied by the macrocyclic skeleton conformation change.

Metalation of Tellurophene: Reactivity of 21,23-Ditelluraporphodimethene toward Palladium(II), Platinum(II), and Rhodium(I).

Ditelluraporphodimethene, a nonaromatic porphyrinoid containing two tellurophene rings, reacted with palladium(II), platinum(II), and rhodium(I) following two different paths. Palladium(II) formed bonds to two tellurium donors of the macrocycle, yielding a side-on coordination compound, with a square planar (Te2Cl2) metal ion environment. An alternative reaction path has been observed for ditelluraporphodimethene with platinum(II) or rhodium(I) in high boiling solvents. These conditions led to the profound transformation, that is, one tellurium atom to a metal atom exchange, resulting in the formation of organometallic species containing metallacyclopentadiene rings, that is, 21-platina-23-telluraporphodimethene and 21-rhoda-23-telluraporphodimethene. The substitution reaction proceeded selectively at the tellurophene ring within the conjugated part of the molecule, that is, the tellurophene ring bound to two sp2 meso-carbon atoms. In the case of platinum, the exchange was accompanied by one meso-aryl ring fusion with the formed platinacyclopentadiene ring, and the platinum(II) macrocycle underwent reversible oxidation with chlorine. The products are stable and represent first nonaromatic examples of metalloporphyrinoids, with a metallacyclopentadiene ring incorporated into a porphodimethene skeleton.

Two Rhodium(III) Ions Confined in a [18]Porphyrin Frame: 5,10,15,20-Tetraaryl-21,23-dirhodaporphyrin.

Invited for the cover of this issue is the group of Ewa Pacholska-Dudziak at the University of Wroclaw. The image depicts two rhodium atoms being fixed into the skeleton of 21,23-dirhodaporphyrin in place of two core nitrogen donors. Read the full text of the article at 10.1002/chem.202201513.

Two Rhodium(III) Ions Confined in a [18]Porphyrin Frame: 5,10,15,20-Tetraaryl-21,23-Dirhodaporphyrin.

Tetraaryl-21,23-dirhodaporphyrin and a series of related monorhodaporphyrins have been obtained by tellurium-to-rhodium exchange in a reaction of tetraaryl-21,23-ditelluraporphyrin with [RhCl(CO)2 ]2 . These organometallic metallaporphyrins contain rhodium(III) centers embedded in rhodacyclopentadiene rings, incorporated within the porphyrin frames. The skeletons of 21,23-dirhodaporphyrin and 21-rhoda-23-telluraporphyrin are strongly deformed in-plane from the rectangular shape typical for porphyrins, due to rhodium(III) coordination preferences, the large size of the two core atoms, and the porphyrin skeleton constrains. These two metallaporphyrins exhibit fluxional behavior, as studied by 1 H NMR and DFT, involving the in-plane motion and the switch of the rhodium center(s) between two nitrogen donors. A side product detected in the reaction mixture, 21-oxa-23-rhodaporphyrin, results from tellurium-to-oxygen exchange, occurring in parallel to the tellurium-to-rhodium exchange. The reaction paths and mechanisms have been analyzed. The title 21,23-dirhodaporphyrin contains a bridged bimetallic unit, Rh2 Cl2 , in the center of the macrocycle, with two rhodium(III) ions lying approximately in the plane of the porphyrinoid skeleton. The geometry of the implanted Rh2 Cl2 unit is affected by macrocyclic constrains.

Chemistry inside a Porphyrin Skeleton: Platinacyclopentadiene from Tellurophene.

Platinum(II) binds to 21,23-ditelluraporphyrin forming a side-on complex, which can be easily transformed into an aromatic metallaporphyrin, that is, 21-platina-23-telluraporphyrin, with a platinacyclopentadiene unit built in the porphyrin skeleton in place of one pyrrole ring. The central platinum(II) ion with a CCNTe square-planar coordination sphere can be oxidized to platinum(IV) by chlorine, bromine, methyl iodide or allyl chloride to yield octahedral complexes. All platinatelluraporphyrins show dynamic behavior involving the platinum ion coordination sphere fluxionality and the porphyrin skeleton deformation, both in-plane and out-of-plane, as demonstrated by 1 H NMR spectroscopy.

28-Hetero-2,7-Naphthiporphyrins: Horizontal Expansion of the m-Benziporphyrin Macrocycle.

Replacement of the m-phenylene moiety of m-benziporphyrins with the 2,7-naphthalenyl subunit yielded 28-hetero-2,7-naphthiporphyrins-macrocycles that can be considered as expanded carbaporphyrinoids. This group retains some features of parent m-benziporphyrins, but due to larger size and different shape of the macrocyclic cavity, their coordination properties are different. Upon reduction and conformational rearrangement the 28-thia- and 28-selena-2,7-naphthiporphyrin form organophosphorus(V) complexes.

Expanded Porphyrin Contraction: From [22]Triphyrin(6.6.0) to [22]Triphyrin(6.5.0).

An expanded triphyrin containing a bipyrrole moiety and annulene links, namely tetraphenyl-[22]triphyrin(6.5.0), 2, has been synthesized. The synthesis proceeded by a postsynthetic transformation of tetraphenyl-[22]triphyrin(6.6.0), 1, in a metal-free unexpected and unprecedented ring contraction during column chromatography on alumina. The observed transformation, located at the hydrocarbon chain linking the pyrrole units, formally corresponds to a subtraction of one carbon atom from an annulene circuit. In contrast to the flexible substrate 1, the product 2 is conformationally rigid, and capable of chloride anion binding in its protonated form.

Shaping a Porphyrinoid Frame by Heteroatoms Extrusion: Formation of an Expanded [22]Triphyrin(6.6.0).

An aromatic expanded triphyrin, [22]triphyrin(6.6.0) 2, containing a pyrrole unit, a bipyrrole moiety, and annulene links, was obtained from a tellurium-containing precursor meso-tetraaryl-26,28-ditellurasapphyrin 1. The reaction path proceeds through an acid-promoted tellurium extrusion from 1 yielding directly 2, characterized in a dicationic form by X-ray crystallography. In solution the neutral macrocycle 2 reveals flexibility typical for annulenes and it exists as a mixture of conformers that differ by the configuration of the annulene fragments, as proven by 1 H NMR studies and analyzed by DFT methods. The conformation is controlled by protonation state, the nature of an interacting anion, solvent identity, and by interaction with water.

Flexible Porphyrinoids.

This review underscores the conformational flexibility of porphyrinoids, a unique class of functional molecules, starting from the smallest triphyrins(1.1.1) via [18]porphyrins(1.1.1.1) and concluding with a variety of expanded porphyrinoids and heteroporphyrinoids, including the 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). The specific flexibility of porphyrinoids has been documented as instrumental in the designing or redesigning of macrocyclic frames, particularly in the search for adjustable platforms for coordination or organometallic chemistry, anion binding, or mechanistic switches in molecular devices. A structural prearrangement to coordinate one or more metal ions has been outlined. The coverage of the topic focuses on representative examples of geometry or conformational rearrangements for each selected class of the numerous porphyrinoids accordingly categorized by the number of built-in carbo- or heterocycles.

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids.

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-electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X-ray structural analyses, and supported by DFT calculations. Although protonation does not change their π-conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32-hetero-5,6-dioxophenanthrisapphyrins.

Incorporation of the 1,5-naphthalene subunit into heteroporphyrin structure: toward helical aceneporphyrinoids.

5,10,15,20-Tetraaryl-22-hetero-1,5-naphthiporphyrins, which contain a 1,5-naphthylene moiety instead of one pyrrole embedded in the macrocyclic framework of heteroporphyrins, were obtained by the [3 + 1] approach using the 1,5-naphthylene analogue of tripyrrane (1,5-bis(phenyl(2-pyrolyl)methyl)naphthalene) and 2,5-bis(arylhydroxymethyl)heterocyclopentadiene (heterocyclopentadiene: thiophene, selenophene, tellurophene). The steric constraints, imposed by the substitution mode of the 1,5-naphthylene building block, resulted in the specific helical conformation of 22-hetero-1,5-naphthiporphyrins. The spectroscopic and structural properties of these aceneporphyrinoids indicate a lack of macrocycle aromaticity. Their protonation yielded solely dicationic species.

The role of nitrogen bridges perturbing the photophysical properties in the porphyrin framework.

We have investigated the photophysical properties of vacataporphyrins possessing systematically controlled butadiene linkers on their π-electron pathways.

Vacata- and divacataporphyrin: new photosensitizers for application in photodynamic therapy-an in vitro study.

BACKGROUND AND OBJECTIVE: The photodynamic therapy is a well-known method of treatment of both malignant tumors and non-tumor lesions in human patients. In the present study, we aimed at evaluating the in vitro efficacy of the new photosensitizing agents, vacataporphyrin (VP), and divacataporphyrin (DVP). MATERIALS AND METHODS: The effectiveness of VP and DVP was compared to well-known photosensitizers, that is, hematoporphyrin derivative (HPD) and chlorin e6 (Ce6) in identical in vitro conditions. The experiment was performed on a well-established breast cancer cell line, MCF-7 and compared to HCV 29T11-2-D1 cell line. Cells were incubated in standard conditions and they were exposed to different concentrations of VP, DVP, HPD, and Ce6, that is, 180, 90, 45, 22.5, and 10 µg/ml. After incubation with photosensitizers, the cells were washed, medium was exchanged and the cells were subjected to irradiation at the proper wavelengths, light intensity (100 mW/sq cm), and total light doses 4.5 and 9 J/sq cm. RESULTS: Our results showed that the VP and DVP are potent photosensitizers and the photocytotoxic effect after the incubation with DVP was much better than that of VP. The cytotoxic effects of VP and DVP were less intensive than these of HPD and Ce6. VP and DVP also accumulated well in the tumor cells. Our results also indicated that the VP and DVP effectiveness on MCF-7 cells was photosensitizer dose and light dose dependent. CONCLUSION: The overall properties revealed by both new porphyrins and particularly a possibility for excitation at a higher wavelength and thus a deeper tissue penetration, make them promising candidates for further in vivo experiments.

Iron(II) vacataporphyrins: a variable annulene conformation inside a regular porphyrin frame.

5,10,15,20-Tetraaryl-21-vacataporphyrin (1), an annulene-porphyrin hybrid containing a butadiene fragment in the macrocycle perimeter, gives paramagnetic iron(II) complexes 2. The porphyrin 1 is devoid of one donor atom of the coordination core; hence, metal ion is bound in the macrocyclic cavity by only three pyrrolic nitrogen atoms. The coordination sphere in 2-X (where X = Cl, Br, I) is completed by a halide anion. The butadiene fragment flexibility and constraints of coordination lead to two stereoisomers with the chain oriented inward (2-i-X) or outward (2-o-X) of the macrocyclic center. Axial halide subtraction (AgBF(4) addition) leads to two new forms differing in the butadiene chain configuration. The (1)H NMR spectra of all complexes show characteristics typical for high-spin iron(II) complexes of porphyrinoids. The dependence of the relaxation times T(1) versus Fe(II)···H distances (estimated by MM+ models) for three of the isomers is in accordance with the in, out, and/or zigzag geometries. The 2-o-X complex is more reactive than 2-i-X and reacts at room temperature with dioxygen to form the iron(II) 21-oxaporphyrin complex, conserving the iron(II) oxidation state. After the addition of imidazole or excess of methanol to a mixture of 2-o-X and 2-i-X, single five-coordinate complexes with out annulene configuration and two axial ligands are formed.

A flexible porphyrin-annulene hybrid: a nonporphyrin conformation for meso-tetraaryldivacataporphyrin.

An annulene-porphyrin hybrid, the diaaza-deficient porphyrin 5,10,15,20-tetraaryl-21,23-divacataporphyrin, has been synthesized by an extrusion of tellurium atom(s) from 5,10,15,20-tetraaryl-21,23-ditelluraporphyrin under treatment with HCl. In addition, a monoaza-deficient 5,10,15,20-tetraaryl-21-tellura-23-vacataporphyrin was formed in the same reaction. The two new members of the vacataporphyrin family were characterized by X-ray crystallography, as well as UV/Vis and NMR spectroscopy. These aromatic molecules preserve the fundamental structural and spectroscopic features of the parent tetraarylporphyrin. The X-ray crystal structures of 21,23-divacataporphyrin and 21-tellura-23-vacataporphyrin show typical porphyrin patterns. The molecules are not strictly planar and show distortion of the annulene moieties. The N22⋅⋅⋅N24 distances (5.23 and 5.09 Å) are considerably longer than in regular porphyrins. For 21,23-divacataporphyrin, variable-temperature (1)H NMR spectroscopy data allowed the identification of divacataporphyrin stereoisomers differentiated by the geometry of the butadiene bridges. The forms remain in thermodynamic equilibrium.

N-fusion approach in construction of contracted carbaporphyrinoids: formation of N-fused telluraporphyrin.

Insertion of PCl(3) into 5,10,15,20-tetraaryl-21-telluraporphyrin leads to a phosphorus complex of N-fused dihydrotelluraporphyrin with an inverted tellurophene ring. Its CNN coordination core places the macrocycle in the family of contracted carbaporphyrinoids. A cycle of direct transformations affords an elegant triangle of three mutually convertible N-fused porphyrinoids, with distinct spectroscopic features: antiaromatic, nonaromatic and aromatic. The nonaromatic species has a dome shaped skeleton which forms in the solid state a ball and socket structure with C(60).

Palladium vacataporphyrin reveals conformational rearrangements involving Hückel and Möbius macrocyclic topologies.

5,10,15,20-Tetraaryl-21-vacataporphyrin (butadieneporphyrin, an annulene-porphyrin hybrid) which contains a vacant space instead of heteroatomic bridge acts as a ligand toward palladium(II). The metal ion of square-planar coordination geometry is firmly held via three pyrrolic nitrogen atoms where the fourth coordination place is occupied by a monodentate ligand or by an annulene part of vacataporphyrin. The macrocycle reveals the unique structural flexibility triggered by coordination of palladium. The structural rearrangements engage the C(20)C(1)C(2)C(3)C(4)C(5) annulene fragment which serves as a linker between two pyrrolic rings of vacataporphyrin albeit the significant ruffling of the tripyrrolic block is also of importance. Two fundamental modes of interactions between the palladium ion and annulene moiety have been recognized. The first one resembles an eta(2)-type interaction and involves the C(2)C(3) unit of the butadiene part. Alternatively the profound conformational adjustments allowed an in-plane coordination through the deprotonated trigonally hybridized C(2) center of butadiene. The coordinated vacataporphyrin acquires Hückel or extremely rare Möbius topologies readily reflected by spectroscopic properties. The palladium vacataporphyrin complexes reveal Hückel aromaticity or Möbius antiaromaticity of [18]annulene applying the butadiene fragment of vacataporphyrin as a topology selector. The properties of specific conformers were determined using (1)H NMR and density functional theory calculations.

Cadmium(II), nickel(II), and zinc(II) complexes of vacataporphyrin: a variable annulene conformation inside a standard porphyrin frame.

5,10,15,20-Tetraaryl-21-vacataporphyrin, 1 (butadieneporphyrin, annulene-porphyrin hybrid), which contains a vacant space instead of heteroatomic bridge, gives diamagnetic zinc(II) 1-ZnCl and cadmium(II) 1-CdCl and paramagnetic nickel(II) 1-NiCl complexes. A metal ion is bound in the macrocyclic cavity by three pyrrolic nitrogens. Coordination imposes a steric constraint on the geometry of the ligand and leads to two stereoisomers with a butadiene fragment oriented toward 1-MCl-i or outward 1-MCl-o of the macrocyclic center. 1-CdCl-o, 1-ZnCl-o, and the free base share a common 1H NMR spectral pattern as the basic structural features of 1 are preserved after metal ion insertion. The 1H NMR spectra of 1-CdCl-i and 1-ZnCl-i reflect a decrease of aromaticity accounted for by the inverted butadiene geometry. The proximity of the butadiene fragment to the metal ion induces direct couplings between the spin-active nucleus of the metal ((111/113)Cd) and the adjacent 1H nuclei of butadiene. The pattern of chemical shifts detected for isomeric 1-NiCl-i and 1-NiCl-o is typical for high-spin nickel(II) complexes of porphyrin analogues. Resonances 2,3-H of 1-NiCl-o or 1-NiCl-i present the chemical shift typical for the beta-H pyrrolic position despite the vacancy in the location of nitrogen-21. Coordination of imidazole, methanol-d4, acetonitrile-d3, or chloride converts 1-NiCl-i and 1-NiCl-o into distinct species which contain two axial ligands: 1-Ni(Im)2+; 1-Ni(CD3OD)2+; 1-Ni(CD3CN)2+; 1-Ni(Cl)2-. The density functional theory (DFT) has been applied to model the molecular and electronic structure of feasible 1-CdCl stereoisomers. The total energies calculated using the B3LYP/LANL2DZ approach demonstrate a very small energy difference (2.3 kcal/mol) between 1-CdCl-o and 1-CdCl-i stereoisomers consistent with their concurrent formation.