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Isoindole-diimine, which can be obtained by bubbling ammonia gas into a solution of phthalonitrile derivatives in the presence of Na[Formula: see text] ion, is a final and best precursor for phthalocyanine synthesis. In this study, isoindole-diimine and various derivatives have been prepared without bubbling ammonia gas using in situ generated ammonia that was produced from formamide and a strong alkali such as NaOH and NaNH2. A longer reaction time, higher temperature, and larger amount of formamide were required for phthalonitrile derivatives with electron-donating groups, but this method is recommendable in that an NH3 gas cylinder and concomitant gas regulator, which are not inexpensive, are not required. Attempts were made to interpret the IR and absorption spectra of the resultant diimines. The signals due to imino proton or N-H of diimino compounds were experimentally found to appear at around 8.2[Formula: see text]9.5 ppm in 1H-NMR and ca. 3500–3000 cm[Formula: see text] in IR spectra.

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

Bicyclo[2.2.2]octadiene(BCOD)-fused dithiaamethyrin 4 was synthesized via a “3+3” condensation method. Thermal conversion of the BCOD moieties afforded tetrabenzodithiaamethyrin 5. The highly planar structures of 4 and 5 were confirmed by X-ray diffraction studies. The 1H NMR, absorption and MCD spectra, together with TD-DFT calculations revealed that both BCOD-fused and [Formula: see text]-extended dithiaamethyrins have a 24[Formula: see text] antiaromatic character.

An ether cleavage reaction of A2B-type subporphyrin bearing an ortho-anisyl substituent afforded a phenolate-bridged dimer. A head-to-tail structure of the dimer was unambiguously elucidated by single crystal X-ray diffraction analysis. UV-vis absorption and magnetic circular dichroism spectra indicated a minor interaction between the subporphyrin chromophores. Density functional theory calculations provided a detailed insight into the electronic structures of the subporphyrin dimer.

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.

Three kinds of silicon phthalocyanine derivatives axially substituted by different groups were prepared and Singledecker-C[Formula: see text]PcSiCl2 (1a), Singledecker-C[Formula: see text]PcSi2(OH)4 (3a, b) and Doubledecker-(C[Formula: see text]PcSi)2Cl2 (4a, b) were obtained in order to investigate their mesomorphism for [Formula: see text] = 8 (a) and 12 (b). The mesomorphism was established by using polarizing microscopic observations, differential scanning calorimetric measurements, temperature-dependent electronic absorption spectra and temperature-dependent X-ray diffraction analysis. From the results, each of the derivatives, 1a, 3a, 3b, 4a and 4b showed columnar mesophases; 1a: Col[Formula: see text](P21/a), pseudo Col[Formula: see text] and Col[Formula: see text]; 3a, b: Col[Formula: see text](P21/a) and Col[Formula: see text]; 4a, b: two kinds of Col[Formula: see text]. Interestingly, each of the virgin samples of singledeckers, C8PcSiCl2 (1a), C8PcSi2(OH)4 (3a) and C8PcSi2(OH)4 (3a), were green in color but changed into blue over ca.180–190 [Formula: see text]C by polymerization. On the other hand, each of the double-deckers, (C[Formula: see text]PcSi)2Cl2derivatives (4a and 4b), decomposed over ca. 180–240[Formula: see text]C. Thus, the influence of the axial groups is so large on their mesomorphism that they exhibit unusual mesomorphic behaviors accompanied by color change.

Electronic structures and direct observation of adlayers on Au(111) of triangular expanded hemiporphyrazines that can be classified into azaporphyrinoids and which can trap three transition metal i...

Mono- and disubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes were successfully prepared, and their in vitro photodynamic activities against MCF-7 breast cancer cells were evaluated with a Thorlabs M660L4 660 nm LED (336 J · cm[Formula: see text]. The IC[Formula: see text] value of the monophenylbuta-1,3-dienylBODIPY was ca. 2.1 [Formula: see text]M, while that of the diphenylbuta-1,3-dienylBODIPY was > 50 [Formula: see text]M. Both dyes exhibited minimal dark toxicity. The results demonstrate that monosubstituted 2,6-dibromo-dimethylaminophenylbuta-1,3-dienylBODIPY dyes merit further in-depth study for use as photosensitizer dyes in photodynamic therapy.

An anionic phthalocyanine derivative, 2,9(10),16(17),23(24)-tetrakis(carboxyl)phthalocyanine copper(II) complex (CuTCPc), exhibited G-quadruplex DNA specific binding. CuTCPc binds selectively to th...

The indium(III) complexes of (4-(tert-butyl)phenyl)-substituted tetraazaisobacteriochlorin (TAiBC) and tetraazachlorin (TAC) were synthesized by direct template condensation of bis(4-(tert-butyl)phenyl)fumaronitrile and tetramethylsuccinonitrile using indium(III) ion as a matrix. The corresponding metal-free tetraazaisobacteriochlorin and tetraazachlorin were obtained by demetallation of their indium(III) complexes. These metal-free complexes were characterized using elemental analysis, mass-spectrometry, 1H and [Formula: see text]C{1H}NMR spectroscopy, UV-vis and MCD spectroscopy as well as DFT and TD-DFT calculations. Due to the low symmetry of the molecules, the NMR data were complex, but could be assigned by collecting 1D- and 2D NMR data and comparing with the results of quantum chemical calculations. From the position of the pyrrole proton signal (6.78 ppm), it was found that the diatropic current of TAiBC is much weaker than that of TAC, and plausibly the weakest among porphyrinoids so far reported. Absorption and MCD spectra were reasonably interpreted using the calculated absorption spectra.

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.

meso-Tetra(3,4,5-trimethoxy)phenyl-porphyrin and -tetrabenzoporphyrin and their phosphorus complexes were synthesized and their electronic absorption and magnetic circular dichroism (MCD) spectra discussed based on TD-DFT molecular orbital (MO) calculations. Nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations were also carried out for metal-free (and phosphorus) tetrabenzoporphyrins in order to discuss the aromaticity and flow of electrons in the molecule.

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

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).

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.

This work is the third part of the review, which presents the properties of a large group of phthalocyanines, which were synthesized and spectroscopically and theoretically studied in works performed under the guidance of the author for the period 2007-2017. Examples of the analysis of spectroscopic data in combination with quantum-chemical calculations of different level are given. As spectroscopic methods, we used the methods of electron absorption, natural and magnetic circular dichroism (CD and MCD) fluorescence, phosphorescence, and electron paramagnetic resonance with time resolution. Based on quantum-chemical calculations, the spectra of (4n + 2) p systems, as well as some 4np antiaromatic systems, were theoretically analyzed. Unlike the first and second parts of the review, this part deals with dimeric and tetrameric systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Optoelectronically active viscous liquids are ideal for fabricating foldable/stretchable electronics owing to their excellent deformability and predictable π-unit–based optoelectronic functions, which are independent of the device shape and geometry. Here we show, unprecedented ‘liquid electret’ devices that exhibit mechanoelectrical and electroacoustic functions, as well as stretchability, have been prepared using solvent-free liquid porphyrins. The fluidic nature of the free-base alkylated-tetraphenylporphyrins was controlled by attaching flexible and bulky branched alkyl chains at different positions. Furthermore, a subtle porphyrin ring distortion that originated from the bulkiness of alkyl chains was observed. Its consequences on the electronic perturbation of the porphyrin-unit were precisely elucidated by spectroscopic techniques and theoretical modelling. This molecular design allows shielding of the porphyrin unit by insulating alkyl chains, which facilitates its corona-charged state for a long period under ambient conditions., Though electret materials are attractive for realizing flexible mechanoelectrical devices, these materials are typically solid films. Here, the authors report stretchable ‘liquid-electret’ devices consisting solvent-free liquid porphyrins that show piezoelectric and electroacoustic functionality.

The second part of the series of review papers on the properties of some synthetically and spectroscopically interesting studies of our group for the period 2007-2017 is presented. In particular, examples of the analysis of spectroscopic data in combination with calculations by the molecular orbitals method are given. We mainly used spectroscopic methods of electron absorption and natural and magnetic circular dichroism, periodically applying fluorescence, phosphorescence and ESR with a time resolution. The spectra of (4n + 2) p systems, as well as some 4np antiaromatic systems, are analyzed theoretically, which helps the reader to interpret the spectral data. In the first and the second parts of this review monomer systems are considered, and in the third - trimeric and tetrameric systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. . .. . . .. .. .. . . . . . . . . . . . . . . .. . . . . . .. . . .. .. . .. . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. . . .. . . . . . . . .. .. . . . . . . .. . . . . . . .. . . .. . . . .. . . .. . . . . . .. . . .. .. . . . . . .. . . . .. . .. .. . .

The conjugation of a symmetrical and an asymmetrical zinc phthalocyanine with amine functionalised cobalt ferrite magnetic nanoparticles (CoFe MNPs) for enhanced photophysics and photocatalysis is reported. The MNPs, 2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato Zn (II) (2) and 2, 10, 16, 24 – tetra 5-(phenoxy)-isophthalic acid phthalocyaninato] Zn (II) (3) as well as their respective conjugates are embedded into electrospun polyamide-6 (PA-6) fibers for support and catalyst regeneration. The resulting photocatalyts (CoFe/PA-6, 2/PA-6, 3/PA-6, CoFe-2/PA-6, and CoFe-3/PA-6) were compared based on their photophysical properties and photocatalytic efficiencies in degrading azo dyes; Methyl Orange (MO) and Orange G (OG). CoFe-2/PA-6 and CoFe-3/PA-6 were found to be more effective photocatalysts than their respective electrospun Pcs and MNPs. The degradation of OG was found to follow pseudo first order kinetics and the Langmuir–Hinshelwood model while that of MO does not.

In this study, novel metal-free, zinc and indium 1(4),8(11),15(18),22(25)-tetramorpholine (1a, 2a, 3a respectively) and 2(3), 9(10), 16(17),23(24)-tetramorpholine (1b, 2b, 3b respectively) phthalocyanines were synthesized and complexes 2 and 3 were quaternized. The photophysical and photochemical properties were investigated in dimethylsulfoxide. The non-peripherally substituted phthalocyanines generated higher singlet oxygen than the peripherally substituted phthalocyanines. Photodynamic antimicrobial chemotherapy activities towards inactivation of Escherichia coli, Staphylococcus aureus and Candida albican were evaluated, where all the quaternized Pcs showed total elimination of the micro-organism with log reductions greater than 9. Though the neutral Pcs had log reductions less than 2, for C. albican the percentage reduction was 68.5% for 2b showing the antifungal properties of the morpholine group.

Condensation of 1,8-diamino-3,6-dichlorocarbazole with a series of disubstituted 1,3-diiminoisoindolines, followed by treatment with BF3 ⋅OEt2 led to the formation of the corresponding core-expanded boron(III) subphthalocyanine analogues. These air-stable π-conjugated boron(III) carbazosubphthalocyanines possess two boron-containing seven-membered-ring units and a 16 π-electron skeleton, and represent the first examples of antiaromatic boron(III) subphthalocyanine analogues as supported by spectroscopic and theoretical studies. The molecular structure of one of these compounds was unambiguously determined by single-crystal X-ray diffraction analysis. In contrast to typical boron(III) subphthalocyanines, which adopt a cone-shaped structure, the π skeleton of this compound is almost planar.

Following the first suggestion of inherent molecular chirality in asymmetrically substituted subphthalocyanines by Torres and co-workers in 2000, elucidation of the relationship between structure and chirality has become an important issue. However, separation of the enantiomers has been prevented by the low solubility of the molecules synthesized to date, and it has not been possible to link the CD signs and intensities to their absolute structures. Recently, we observed that 1,2-subnaphthalocyanines possess two diastereomers with respect to the arrangement of the naphthalene moieties and that these novel chiral molecules exhibit moderate solubility in common organic solvents. This has enabled us to separate all of the diastereomers and enantiomers. The two diastereomers have been completely characterized by NMR spectroscopy and X-ray diffraction analysis. The absorption and magnetic circular dichroism spectra, together with theoretical calculation, reveal a small variation in the frontier molecular orbitals of the 1,2-subnaphthalocyanines compared with conventional subphthalocyanines, except for destabilization of the HOMO–3, which results in a characteristic absorption in the Soret band region. The chirality of 1,2-subnaphthalcyanines, including the CD signs and intensities, is discussed in detail for the first time with enantiomerically pure molecules whose absolute structures have been elucidated by single-crystal X-ray diffraction analysis.

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.

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.

A kinematically complete quasifree (p,pn) experiment in inverse kinematics was performed to study the structure of the Borromean nucleus ^{17}B, which had long been considered to have a neutron halo. By analyzing the momentum distributions and exclusive cross sections, we obtained the spectroscopic factors for 1s_{1/2} and 0d_{5/2} orbitals, and a surprisingly small percentage of 9(2)% was determined for 1s_{1/2}. Our finding of such a small 1s_{1/2} component and the halo features reported in prior experiments can be explained by the deformed relativistic Hartree-Bogoliubov theory in continuum, revealing a definite but not dominant neutron halo in ^{17}B. The present work gives the smallest s- or p-orbital component among known nuclei exhibiting halo features and implies that the dominant occupation of s or p orbitals is not a prerequisite for the occurrence of a neutron halo.

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 re...

Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates ((Bu)PcLn(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 ((tBuPh)DzPzH(2), 2) produced sandwich compounds ((tBuPh)DzPz)Ln(Pc-Bu) (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 H-1 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 H-1-H-1 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 Pc(2)Ln compounds.

The formation of a dineutron in the nucleus $^{11}$Li is found to be localized to the surface region. The experiment measured the intrinsic momentum of the struck neutron in $^{11}$Li via the $(p,pn)$ knockout reaction at 246 MeV/nucleon. The correlation angle between the two neutrons is, for the first time, measured as a function of the intrinsic neutron momentum. A comparison with reaction calculations reveals the localization of the dineutron at $r\sim3.6$ fm. The results also support the density dependence of dineutron formation as deduced from Hartree-Fock-Bogoliubov calculations for nuclear matter.

The heaviest bound isotope of boron ^{19}B has been investigated using exclusive measurements of its Coulomb dissociation, into ^{17}B and two neutrons, in collisions with Pb at 220 MeV/nucleon. Enhanced electric dipole (E1) strength is observed just above the two-neutron decay threshold with an integrated E1 strength of B(E1)=1.64±0.06(stat)±0.12(sys) e^{2} fm^{2} for relative energies below 6 MeV. This feature, known as a soft E1 excitation, provides the first firm evidence that ^{19}B has a prominent two-neutron halo. Three-body calculations that reproduce the energy spectrum indicate that the valence neutrons have a significant s-wave configuration and exhibit a dineutronlike correlation.

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.

Spectroscopic factors of neutron-hole and proton-hole states in 131Sn and 131In, respectively, were measured using one-nucleon removal reactions from doubly magic 132Sn at relativistic energies. For 131In, a 2910(50)-keV γ ray was observed for the first time and tentatively assigned to a decay from a 5=2− state at 3275(50) keV to the known 1=2− level at 365 keV. The spectroscopic factors determined for this new excited state and three other single-hole states provide first evidence for a strong fragmentation of singlehole strength in 131Sn and 131In. The experimental results are compared to theoretical calculations based on the relativistic particle-vibration coupling

Spectroscopy of 16B plays an essential role in understanding the halo structure in 17B, but very limited knowledge has so far been obtained. We have carried out a kinematically complete measurement on the spectroscopy of 16B by using quasi-free (p,pn) reaction on 17B. The level scheme of 16B up to 5 MeV was made clear for the first time.

Porphyrins are functional elements of important biomolecules, whose assemblies play a central role in fundamental processes such as electron transfer, oxygen transport, enzymatic catalysis, and light harvesting. Here we report an approach to formation of porphyrin supermolecules, a particular type of nanoparticles with unusually strong noncovalent intermolecular interactions. Key differences between the supermolecules and noncovalent nanostructures described earlier are as follows. (1) Supermolecules consist of molecules of the same type without side groups promoting the self-assembly and without any spacers; no surfactant or catalyst to assist the process is needed. (2) They exhibit unusual photophysical properties and remain stable even in organic solvents. Their formation occurs under specially selected conditions at the air-water interface at room temperature. Following this route, we have formed supermolecules of magnesium porphine, a functional element of chlorophyll. The properties of these supermolecules are markedly different from those of the constituent molecules. For example, in contrast to the pink color of the monomer solution, solutions of supermolecules are transparent for visible light and absorb in the ultraviolet and near-infrared regions. We also present atomic force microscopy visualization of the porphyrin two-dimensional nanoaggregates forming at the air-water interface that were predicted in our previous works. This approach offers a guideline for the discovery of new supermolecules, including complex biological ones, and the formation of supermolecular materials with novel properties.