The windmill, the dragon, and the frog: geometry control over the spectral, magnetic, and electrochemical properties of cobalt phthalocyanine regioisomers.

For the first time, we have prepared non-aggregating phthalocyanine cobalt complexes as a set of resolved positional isomers. These compounds comprise a unique test bed for the structure-properties studies, as their optical and electrochemical properties are influenced by the planarity of the phthalocyanine macrocycle, which can be controlled by the positional isomerism of the bulky aromatic substituents at the α-phthalo sites. We support our conclusions with molecular modelling studies, which show a perfect match between the calculated and experimentally determined spectral/electrochemical values. We challenge a common perception that the NMR spectra of cobalt phthalocyanines cannot be measured due to the paramagnetic nature of Co(II). We suggest instead that the key factors affecting the NMR spectral resolution are molecular aggregation and π-π stacking. These interactions are suppressed by the bulky peripheral substituents on the cobalt phthalocyanines prepared, making these isomeric compounds an excellent tool for paramagnetic NMR studies.

Phosphorus(V) Tetraazaporphyrin with an Intense, Broad CT Band in the Near-IR Region.

In phosphorus tetraazaporphyrins (PTAPs), the Q- and charge-transfer (CT) bands appear as a result of configuration interaction between their excited states. On the basis of this concept, a PTAP with an intense, broad CT band in the near-IR region has been rationally designed and realized by introducing eight diphenylaminophenyl (dPAP) groups. The order of the CT and Q-bands in ascending energy was supported by magnetic circular dichroism (MCD) spectroscopy and theoretical calculations. An intense two-photon absorption was also found in the deep near-IR region.

Synthesis of Cross-Chain Bridging Cryptands and Induction of Molecular Chirality.

In this study, we synthesized two cryptands featuring entangled tri- and tetra(ethylene glycol) linkers. The cryptand bearing short linkers was chiral without any asymmetric carbon atoms. After chiral high-performance liquid chromatography was used to separate the enantiomers, the absolute configuration of each cryptand was determined through single-crystal X-ray and circular dichroism analyses. The racemization of the cryptand possessing long linkers proceeded at room temperature.

Synthesis of Peripherally Annulated Phenanthroporphyrins.

Synthesis of unusual phenanthroporphyrins was achieved by a stepwise precursor method. Precursor porphyrins fused with aryl-substituted bicyclo[2.2.2]octadiene afforded the corresponding arylbenzoporphyrins (arylBPs) by a retro Diels-Alder reaction. Unusual phenanthroporphyrins were obtained via the intramolecular Scholl reaction of arylBPs. X-ray crystallographic analysis revealed a distorted, helical porphyrin plane. Red-shifted absorptions of tetraphenanthroporphyrin are observed at ca. 580 nm for the B band and at 700-900 nm for the Q bands. Analysis of magnetic circular dichroism spectra and time-dependent density functional theory calculations was used to explain the optical properties and electronic structures.

Iron-Catalyzed Biomimetic Dimerization of Tryptophan-Containing Peptides.

Biomimetic oxidative dimerization of tryptophan derivatives in aqueous media with oxygen as a bulk oxidant catalyzed by an iron octacarboxy phthalocyanine complex was established. The discovery of the extremely active iron catalyst enables aerobic enzyme-mimetic oxidation to be performed in a flask. This method was applicable to the oxidative dimerization of a wide range of tryptophan derivatives, including various dipeptides and oligopeptides, with remarkable functional-group tolerance without the protection of the amino acid residues. Furthermore, oxidative dimerization of tryptophan derivatives bearing dioxopiperazine units enabled the convergent total synthesis of five natural pyrroloindole compounds and unnatural congeners. The established chemical method provides facile access to a broad range of dimerized peptides with a unique scaffold to link two turn structures, which will serve as a powerful tool to create new small- and medium-sized-molecules as drug candidates.

Supermolecular Nanoentities of Vitamin B12 Derivative as a Link in the Evolution of the Parent Molecules During Self-Assembly at the Air-Water Interface.

Nanoarchitectures with promising properties have now been formed from many important biomolecules. However, the preparation of nanoparticles of vitamin B12 and its derivatives remains an ongoing research challenge. This paper describes the formation of supermolecular nanoentities (SMEs) of vitamin B12 derivatives, unique nanoparticles with strong noncovalent intermolecular interactions, emerging properties, and activity. These were created by a nanoarchitectonic approach using directed assembly of layers at the air-water interface as a link in the chain of evolution of the parent molecules under specially created conditions. Such layers can be represented as a nanocosm, where, at a critical density, the assemblies act as nanoreactors in which the transformation of the original material occurs. The discovered SMEs not only replicate the functioning of vitamin B12 assemblies with proteins in living organisms and act as vitamin B12-depended enzymes but also demonstrate important advantages over vitamin B12. They are more efficient in oxygen reduction/evolution reactions and in transformation into other forms. These SMEs, in performing advanced tasks, are an alternative to widely used materials based on noble metals for catalysis, medicine, and environment protection. Our findings open new perspectives both for the fabrication of novel SMEs of biomolecules and for a better understanding of the evolution of biomolecules in nature.

Dianion and Dication of Tetracyclopentatetraphenylene as Decoupled Annulene-within-an-Annulene Models.

The dianion and dication of tetramesityl-substituted tetracyclopentatetraphenylene, a circulene consisting of alternating five- and six-membered rings, have been generated by reduction with alkali metals and oxidation with antimony(V) halides, respectively. They are theoretically predicted to adopt double annulenoid structures called annulene-within-an-annulene models in which the outer and inner conjugation circuits are significantly decoupled. The theoretical structures were experimentally proven by X-ray crystallographic analyses and the electronic configurations were supported by MCD spectra. Based on the 13 C NMR chemical shifts, negative and positive charges are shown to be located mainly at the outer periphery, indicating that the dianion and dication have delocalized 22-π and 18-π electron outer perimeters, respectively, and 8-π electron structure at the inner ring. Notably, the dianion has an open-shell character, whereas the dication has a closed-shell ground state.

Synthesis of Non- or Antiaromatic Dicarbaamethyrin: [24]Diazulihexaphyrin(0.1.0.0.1.0).

A "3+3" condensation reaction of 1,3-di(2-pyrrolyl)azulene with aryl aldehyde followed by an oxidative aromatization afforded diazuliamethyrin, [24]diazulihexaphyrin(0.1.0.0.1.0). X-ray diffraction analysis revealed a relatively planar structure of diprotonated diazuliamethyrin with a mean plane deviation of 0.37 Å. A 24π non- or antiaromatic character was confirmed by 1H NMR, absorption, MCD spectra, and TD-DFT calculations that included the NICS values and ACID plots.

Synthesis of a Mechanically Planar Chiral and Axially Chiral [2]Rotaxane.

In this study, we synthesized a [2]rotaxane that was both mechanically planar chiral and axially chiral, comprising a symmetrical bis-crown ether featuring a biphenyl moiety (as the macrocyclic component) and a symmetrical bis-ammonium salt (as the dumbbell-shaped component).

Phenanthroline-Fused Phthalocyanine Analogues Having a Monovalent Corrole Inner Perimeter and 4nπ Nonaromatic Properties.

Condensation of 4,5-bis(4-tert-butyl-2,6-dimethylphenoxy)phthalonitrile with 2,9-diamino-1,10-phenanthroline in the presence of M(OAc)2 (M = Ni, Pd, Zn) afforded a series of phenanthroline-fused phthalocyanine analogues with a 16 π-electron skeleton. While the arrangement of elements along the inner perimeter of these macrocycles is the same as that of the hitherto reported trivalent corroles, they represent the first example of porphyrinoids possessing a monovalent corrole inner perimeter and nonaromatic characteristics as revealed by their spectroscopic data and theoretical studies.

Cyclo[9]pyrrole: Selective Synthesis of [34]Nonaphyrin(0.0.0.0.0.0.0.0.0).

Cyclo[9]pyrrole, a ring-expanded porphyrin without meso-bridges and having an odd number of pyrroles, was synthesized via the oxidative coupling of 2,2':5',2″-terpyrrole. X-ray crystallography showed a C2-like symmetry with a large root-mean-square deviation. The optical properties and electronic structures were analyzed using magnetic circular dichroism spectroscopy and time-dependent density functional theory calculations.

Synthesis and characterization of heteroleptic rare earth double-decker complexes involving tetradiazepinoporphyrazine and phthalocyanine macrocycles.

Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates (BuPcLn(acac), 1a-c, Ln = Lu (a), Eu (b), La (c)) with a tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand (tBuPhDzPzH2, 2) produced sandwich compounds (tBuPhDzPz)Ln(BuPc) (3a-c), which represent the first heteroleptic double-deckers incorporating both Pc and DzPz decks. A combination of high-resolution mass spectrometry, UV-Vis/NIR, MCD, and 1H NMR spectroscopy, and square-wave voltammetry provided unambiguous characterization of target complexes 3 indicating that their spectral and electrochemical properties are generally intermediate with respect to their homoleptic relatives. Based on the data of solution-state 1H-1H NMR (COSY, NOESY) correlation spectroscopy supported by DFT calculations, a dimerization tendency of compounds 3 proportional to the Ln(iii) ion size was found. The spectroelectrochemical study of 3 and the corresponding homoleptic double-deckers revealed a pronounced tendency to aggregation of the one-electron oxidized forms of DzPz-containing double-decker complexes compared to homoleptic Pc2Ln compounds.

A Chiral [3]Rotaxane Comprising Achiral Bis-macrocyclic and Dumbbell-Shaped Components.

In this study, we synthesized a molecularly chiral [3]rotaxane comprising a calix-bis-crown ether (as the macrocyclic component) and two unsymmetrical dialkylammonium salts (as dumbbell-shaped components) without any chirality in any of the individual components. Chiral high-performance liquid chromatography was used to separate the enantiomers, which were characterized by circular dichroism spectroscopy. Density functional theory calculations gave an insight into the absolute configuration of each [3]rotaxane.

Periphery-Fused Chiral A2B-Type Subporphyrin.

Despite significant interest, the chiroptical properties of subporphyrins have rarely been investigated because chiral subporphyrins are elusive. Here, inherently chiral subporphyrins are elaborated by forming a fused pyran ring at the periphery of an A2B-type meso-aryl-substituted subporphyrin. Their circular dichroism (CD) properties are largely affected by the peripheral substituents and the dihedral angles between the meso-aryl substituents and the subporphyrin core: the ß-perbromo subporphyrin with an orthogonal arrangement of the meso-phenyl substituents to the subporphyrin core exhibits weak CD signals corresponding to the Q bands, whereas the unsubstituted species with smaller dihedral angles shows relatively intense CD signals. A detailed structure-property relationship of these chiral subporphyrins was elucidated by time-dependent (TD) DFT calculations. This study reveals that the CD properties of chiral subporphyrins can be controlled by peripheral substitution and meso-aryl substituents.

Synthesis and Characterization of Peralkylated Pyrrole-Fused Azacoronene.

A hexapyrrolohexaazacoronene (HPHAC) with 12 less-bulky peripheral ethyl groups than its aryl-containing HPHAC counterpart was synthesized to investigate the innate character of HPHAC. X-ray diffraction analysis revealed that HPHAC had a planar structure and close packing because of CH-π interactions between the alkyl groups and the HPHAC core. Compared to the previously reported HPHAC decorated with 12 peripheral aryl groups, this electron-rich π-system exhibited reversible multistep oxidations at low potentials and easily formed mono- and dicationic salts and charge-transfer (CT) complexes with 7,7,8,8-tetracyano-p-quinodimethane. These oxidized species exhibited clear changes in the bond-length alternation of the pyrrole units in the crystal state, indicating charge and spin delocalization. The distinct upfield shift of the central carbon signal of the dication in the 13C NMR spectrum affirms the global aromaticity from the viewpoint of a magnetic criterion. In the UV-vis/NIR spectra, broad absorption in the NIR region was observed only for HPHAC2+ and not the structurally similar cyclo[6]pyrrole. Magnetic circular dichroism measurements and time-dependent density functional theory calculations revealed that the broad absorption was assigned to the CT transition from the central benzene ring to the outer pyrrole rings.

Radially π-Extended Pyrrole-Fused Azacoronene: A Series of Crystal Structures of HPHAC with Various Oxidation States.

Radially π-extended hexapyrrolohexaazacoronene (HPHAC 2) was synthesized in two steps with 2,5-di-tert-butyl-acenaphtho[1,2-c]pyrrole and hexafluorobenzene. Like its parent HPHAC 1a, 2 exhibited reversible oxidation behavior. Crystal structures of not only the neutral and dicationic compounds but also the radical cation were all revealed. While analyzing its peculiar structure, the formation of a 1:1 complex with C60 was observed in solution by NMR and absorption analyses. The spectroscopic analyses of 2 and 1a were performed based on magnetic circular dichroism and theoretical calculations.

Recent Progress in Optically-Active Phthalocyanines and Their Related Azamacrocycles.

Optically-active phthalocyanines (Pcs) and related macrocycles reported in the 2010-2020 period are introduced in this review. They are grouped into several categories: (1) chiral binaphthyl-containing Pcs, (2) optically active alkyl chain-containing Pcs, (3) chiral axial ligand- coordinated or -linked Pcs, (4) chiral subphthalocyanines (SubPcs), and (5) related azamacrocycles. For each compound, the structure and important characteristics are summarized.

TTF-Annulated Silicon Phthalocyanine Oligomers and Their External-Stimuli-Responsive Orientational Ordering.

Orientational control of functional molecules is essential to create complex functionalities as seen in nature; however, such artificial systems have remained challenge. Herein, we have succeeded in controlling rotational isomerism of µ-oxo silicon phthalocyanine (SiPc) oligomers to achieve an external-stimuli-responsive orientational ordering using intermolecular interactions of tetrathiafulvalene (TTF). In this system, three modes of orientations, free rotation, eclipsed conformation, and staggered conformation, were interconverted in response to the oxidation states of TTF, which varied interactions from association due to formation of mixed-valence TTF dimer to dissociation due to electrostatic repulsion between TTF dications. Furthermore, a stable performance of oligomers as a cathode material in a Li-ion battery proved that the one-dimensionally stacked, rotatable structure of SiPc oligomers is useful to control the orientation of functional molecules toward molecular electronics.

Synthesis and Aromaticity of Benzene-Fused Doubly N-Confused Porphyrins.

A bicyclo[2.2.2]octadiene(BCOD)-fused bis(dipyrromethane) derivative was reacted with methylal in the presence of trifluoroacetic acid followed by oxidation with chloranil to give a doubly N-confused phlorin derivative, which did not undergo the retro-Diels-Alder reaction extruding an ethylene molecule on heating. In contrast, a 7-tert-butoxybicyclo[2.2.1]heptadiene(7-BuOBCHD)-fused bis(dipyrromethane) yielded benzene-ring-fused doubly N-confused porphyrins by following similar reaction sequences.

Preparation, Spectroscopic Characterization and Theoretical Study of a Three-Dimensional Conjugated 70 π-Electron Thiophene 6-mer Radical Cation π-Dimer.

A radical cation, generated from an extended π-conjugated thiophene 6-mer composed of four ethynylene-thienylene and two vinylene-thienylene units, was observed to form a stable three-dimensional π-dimer containing 70 π-electrons. The π-dimer prepared in solution was investigated by using magnetic circular dichroism (MCD), ESR spectroscopy, and UV-vis-NIR absorption spectroscopy. Probing the individual NIR absorption bands showed that the MCD signals can be assigned to the pseudo Faraday A term, indicating that the absorption bands are comprised of nearly degenerate electronic transitions. X-ray crystallographic analysis revealed that the π-dimer has a three-dimensional face-to-face and continuous π-conjugated donutlike structure. Analysis of the UV-vis-NIR and ESR spectra of the π-dimer in the solid state confirmed that it possesses the dimer structure. The prediction made by using TD-DFT calculations that the dimer would have a 70 π-electron diatropic nature was confirmed by using solid state 1H NMR spectroscopy.