Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters.

Recently, pyrrole cages have been synthesized that encapsulate ion pairs and silver(I) clusters to form intricate supramolecular capsules. We report here a computational analysis of these structures using density functional theory combined with a semiempirical tight-binding approach. We find that for neutral pyrrole cages, the Gibbs free energies of formation provide reliable predictions for the ratio of bound ions. For charged pyrrole cages, we find strong argentophilic interactions between Ag ions on the basis of the calculated bond indices and molecular orbitals. For the cage with the Ag4 cluster, we find two minimum-geometry conformations that differ by only 6.5 kcal/mol, with an energy barrier <1 kcal/mol, suggesting a very flexible structure as indicated by molecular dynamics. The predicted energies of formation of [Agn⊂1]n-3+ (n = 1-5) cryptands provide low energy barriers of formation of 5-20 kcal/mol for all cases, which is consistent with the experimental data. Furthermore, we also examined the structural variability of mixed-valence silver clusters to test whether additional geometrical conformations inside the organic cage are thermodynamically accessible. In this context, we show that the time-dependent density functional theory UV-vis spectra may potentially serve as a diagnostic probe to characterize mixed-valence and geometrical configurations of silver clusters encapsulated into cryptands.

Iminopyrrole-Based Self-Assembly: A Route to Intrinsically Flexible Molecular Links and Knots.

The use of 2,5-diformylpyrrole in self-assembly reactions with diamines and Zn(II)/Cd(II) salts allowed the preparation of [2]catenane, trefoil knot, and Borromean rings. The intrinsically dynamic nature of the diiminopyrrole motif rendered all of the formed assemblies intramolecularly flexible. The presence of diiminopyrrole revealed new coordination motifs and influenced the host-guest chemistry of the systems, as illustrated by hexafluorophosphate encapsulation by Borromean rings.

Tying a knot between crown ethers and porphyrins.

Porphyrins and crown ether hybrids have emerged as a promising class of molecules composed of elements of a tetrapyrrole macrocycle and an oligo(ethylene glycol) segment. These hybrid systems constitute a broad group of compounds, including crowned porphyrins, crownphyrins, and calixpyrrole-crown ether systems forming Pacman complexes with transition metals. Their unique nature accustoms them as excellent ligands and hosts capable of binding guest molecules/ions, but also to undergo unusual transformations, such as metal-induced expansion/contraction. Depending on the design of the particular hybrid, they present unique features involving intriguing redox chemistry, interesting optical properties, and reactivity towards transition metals. In this perspective article, the overview of both the early designs of porphyrin-crown ether hybrids, as well as the most recent advances in the synthesis and characterisation of this remarkable group of macrocyclic systems, are addressed. The discussion covers the strategies employed in synthesising these systems, including cyclisation reactions, self-assembly, and their remarkable reactivity. The potential applications of porphyrin-crown ether hybrids are also highlighted. Moreover, the discussion identifies the challenges associated with synthesising and characterising hybrids, outlining the possible future directions.

The Intracavity Extension of 28-Hetero-2,7-naphthiporphyrins in Reactions with Alkylamines.

The 28-hetero-2,7-naphthiporphyrins reacted with triethylamine and diethylamine to form nonaromatic intracavity-extended macrocycles incorporating naphthodihydro-2H-pyran, naphthotetrahydropyridine, and naphthopyrrolotetrahydro-1H-azepine moieties. The new macrocycles were characterized in solution by means of NMR and UV-vis spectroscopy and in the solid state by XRD.

POSSaxanes: active-template synthesis of organic-inorganic rotaxanes incorporating cubic silsesquioxane stoppers.

The CuAAC active-template approach was exploited to construct rotaxanes incorporating cage-like silsesquioxane stoppers, namely, POSSaxanes. The compounds were characterized in the solution and solid state, providing the unprecedented molecular structures of POSS-incorporating rotaxanes.

Plenates: Anion-Dependent Self-Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters.

The self-assembly of 2,5-diformylpyrrole, tris(2-aminoethyl)amine, and silver(I) yielded, depending on the size and basicity of the anion, new cascade complexes or plenates, that is, cryptates incorporating Agn n+ clusters. The nature of the product was counterion-dependent, and its formation was either driven by cascade anion binding or by argentophilic interactions stabilizing the cluster within the cavity. The reaction of plenates with tetrabutylammonium halides resulted in the protonation-coupled replacement of the Ag3 3+ with anion(s), yielding cascade cryptates.

Crownphyrins: Metal-Mediated Transformations of the Porphyrin-Crown Ether Hybrids.

Crownphyrins are hybrid macrocycles combining structural features of porphyrin and crown ethers. The molecular architecture renders them an intriguing class of hosts capable of binding neutral, and ionic guests. The presence of dynamic covalent imine linkages connecting the dipyrrin segment with the ether chain enables unusual coordination behavior of crownphyrins, as demonstrated by the formation of two classes of strikingly different complexes. The remarkable metal-mediated expansion to the helical [2+2] macrocyclic complex is reversible. The reaction of the figure-eight mercury(II) assembly with [2.2.2]cryptand results in ring contraction providing the metal-free crownphyrin macrocycle.

Two-photon absorption of 28-hetero-2,7-naphthiporphyrins: expanded carbaporphyrinoid macrocycles.

The one- and two-photon absorption (1PA and 2PA) properties of three expanded aceneporphyrinoids, 28-thia-, 28-selena- and 28-tellura-2,7-naphthiporphyrin, have been studied. The open-aperture Z-scan technique was used to determine two-photon absorption cross-sections in the near infrared range using an amplified femtosecond laser system. The maximum values of the cross sections were found to be 99, 200 and 650 GM at 900 nm and 1, 13 and 31 GM at 1400 nm for the three investigated compounds, respectively. These results demonstrate enhanced 2PA properties compared with well-known porphyrin photosensitizers, such as Foscan®, showing the potential of porphyrin core modification for optimizing infrared nonlinear absorbers.

Conformation-Dependent Response to the Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): A Route to Pseudorotaxane-Like Structures.

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 in multiple conformational rearrangements and anion-binding events. The formation of one of the final dicationic forms is accompanied by the inclusion of a complex anion(s) within the macrocyclic cavity yielding a pseudorotaxane-like host-guest complex. Protonation with trifluoroacetic or dichloroacetic acids followed by neutralization afforded a conformation-switching cycle, which involves six structurally different species. Analogous acidification with chiral 10-camphorsulfonic acid and subsequent neutralization generated one of the free base stereoisomers with enantiomeric excess. Therefore, it was shown that the simple acid-base chemistry of diphenanthrioctaphyrin can act as stimulus, inducing chirality into the system, allowing for the manipulation of the stereochemical information imprinted into the enantiomers of the macrocycle.

Kinetic versus Thermodynamic Control Over Multiple Conformations of Di-2,7-naphthihexaphyrin(1.1.1.1.1.1).

Di-2,7-naphthihexaphyrin(1.1.1.1.1.1), a non-aromatic carba-analogue of the hexaphyrin(1.1.1.1.1.1), incorporating two built-in 2,7-naphthylene moieties was synthesized as two separate, conformationally locked stereoisomers. Both conformers followed complex protonation pathways involving structurally different species, which can be targeted under kinetic and thermodynamic control. The neutralization of the ultimate dicationic product, accessible from both stereoisomers of the free base, allowed to realize the complex conformational switching cycle involving six structurally different species.

Expanded Carbaporphyrinoids.

This Review outlines the progress in the field of synthetic expanded carbaporphyrinoids. The evolution of this topic is demonstrated with expanded porphyrin-inspired systems with a variety of incorporated entities that introduce one or more carbon atoms into the cavity. The discussion starts with platyrins-the macrocycles that were identified as parent molecules of not only the expanded carbaporphyrinoids, but the carbaporphyrinoid class in general. After historic considerations, the plethora of expanded porphyrin-like macrocycles containing N-confused or neo-confused pyrrole motifs and different carbocyclic subunits are presented. Special emphasis is given to applications of expanded carbaporphyrinoids in different areas, including organometallic chemistry, switching systems, or aromaticity, concluding with the demonstration of a covalent cage based on an expanded carbaporphyrinoid.

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.

Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): Conformational Switching Controls the Stereochemical Dynamics of the Topologically Chiral System.

The analogue of octaphyrin(1.1.1.0.1.1.1.0) bearing two dimethoxyphenanthrene units was synthesized and characterized in solution and solid state. The macrocycle was demonstrated to exist as two locked conformers that can be easily separated and handled individually. The conversion of conformers was proven to be facilitated by the presence of hydrogen-bond acceptors, such as amines. The bis-boron(III) complex of diphenanthrioctaphyrin has been obtained, proving that the metalloid center acts as the topology selector stabilizing only one conformation of the macrocycle, irrespective of the stereoisomer used for the insertion. Both conformers of diphenanthrioctaphyrin, as well as the boron complex formed from them, have been separated into enantiomers using HPLC with a chiral stationary phase. All of these systems have shown strikingly different stereodynamic behavior.

Organocopper(III) Phenanthriporphyrin-Exocyclic Transformations.

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 substituents attached to two trans meso positions. Addition of acids to 1-Cu yields two isomeric copper(III) isophenanthriporphyrins protonated on one of the meso carbon atoms. Protonation of copper(III) 5,6-dioxophenanthriporphyrin 2-Cu yields the aromatic diprotonated complex 2-Cu-H22+. In the presence of HBF4 2-Cu undergoes borylation at the carbonyl oxygen atoms, forming an aromatic exocyclic boron(III) complex.

Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S-Shaped Aza[5]helicene Motifs.

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.

Sequence-selective encapsulation and protection of long peptides by a self-assembled FeII8L6 cubic cage.

Self-assembly offers a general strategy for the preparation of large, hollow high-symmetry structures. Although biological capsules, such as virus capsids, are capable of selectively recognizing complex cargoes, synthetic encapsulants have lacked the capability to specifically bind large and complex biomolecules. Here we describe a cubic host obtained from the self-assembly of FeII and a zinc-porphyrin-containing ligand. This cubic cage is flexible and compatible with aqueous media. Its selectivity of encapsulation is driven by the coordination of guest functional groups to the zinc porphyrins. This new host thus specifically encapsulates guests incorporating imidazole and thiazole moieties, including drugs and peptides. Once encapsulated, the reactivity of a peptide is dramatically altered: encapsulated peptides are protected from trypsin hydrolysis, whereas physicochemically similar peptides that do not bind are cleaved.

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.

Core chemistry and skeletal rearrangements of porphyrinoids and metalloporphyrinoids.

Core alteration, affording heteroporphyrinoids and carbaporphyrinoids, allows for the exploration of porphyrin-like or porphyrin-unlike coordination chemistry. Such a strategy has provided a fundamental change in the approach to macrocyclic organometallic chemistry. The specific reactivity of porphyrinoids has offered an insight into reactions inside particularly shaped macrocyclic architecture, including metal-mediated organic transformations. This review focuses on alterations of macrocycles, made of four carbocyclic/heterocyclic subunits, which resemble the structure of porphyrin or porphyrin isomers, providing, however, remarkable porphyrin-like (XNNN), (CNNN), (CNCN) or (C2NNN) surroundings. To facilitate the understanding of the discussed subject matter, all addressed reactions reflecting core reactivity have been formally grouped into nine categories distinguished by the principal type of transformation addressed: (1) alkylation or arylation, (2) core heteroatom replacement, (3) oxidation and oxygenation, (4) substitution, (5) macrocyclic fusion, (6) core bridging, (7) ring contraction, (8) ring expansion, and (9) C-H and C-C bond activation. The distinctive macrocyclic environment creates a long-sought opportunity to trap unique organometallic transformations which include instances of benzene ring contraction to cyclopentadiene or the formation of an unprecedented metalloporphyrinoid: 21-pallada-23-telluraporphyrin. This review offers certain challenging perspectives which target the goals of organometallic bond activation.

Phenanthriporphyrin: an antiaromatic aceneporphyrinoid as a ligand for a hypervalent organophosphorus(V) moiety.

The incorporation of a phenanthrene moiety into a porphyrin framework results in the formation of a hybrid macrocycle­phenanthriporphyrin­merging the structural features of polycyclic aromatic hydrocarbons and porphyrins. An antiaromatic aceneporphyrinoid, adopting the trianionic {CCNN} core, is suitable for the incorporation of a phosphorus(V) center to form a hypervalent organophosphorus(V) derivative.