Tatsuhisa Kato

• Kyoto 606-8501, Japan
• Senior Researcher at Kyoto University

Mono‐alkene‐inserted [n]cycloparaphenylenes 1 [(ene)‐[n]CPP] with n=6, 8, and 10, mono‐ortho‐phenylene‐inserted [6]CPP 2, and di‐alkene‐insertved [n]CPP 3 [(ene)2‐[n]CPP] with n=4, 6, and 8 were synthesized by fusing CPP precursors and alkene or ortho‐ phenylene groups through coupling reactions. Single‐crystal X‐ray diffraction analyses reveal tha...

Mono‐alkene‐inserted [N]cycloparaphenylenes 1 [(ene)‐[N]CPP] with N = 6, 8, and 10, mono‐ortho‐phenylene‐inserted [6]CPP 2, and di‐alkene‐inserted [N]CPP 3 [(ene)2‐[N]CPP] with N = 4, 6, and 8 were synthesized by fusing CPP precursors and alkene or ortho‐ phenylene groups via coupling reactions. Single‐crystal X‐ray diffraction analyses reveal that...

The flexibility of the bridging alkyl chains is important for proximity in the stacking of porphyrin and phthalocyanine conjugated through a fourfold rotaxane linkage. This picture shows a chochin, a Japanese lantern made with paper and thin strips of bamboo that can be expanded and contracted flexibly. This foldability recalls the induced molecula...

Invited for the cover of this issue are Kentaro Tanaka at Nagoya University and co‐workers. The image depicts the importance of the flexibility of bridging alkyl chains in a molecular conjugate to pack the components closely to generate efficient molecular communication. Read the full text of the article at 10.1002/chem.202200819.

Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linka...

We designed peptides that formed helix bundle structures upon binding of the metal-ions to His residues to form a stable hydrophobic core, in order to analyze the effects of Ala, Val, Ile, and Leu residues, located in the hydrophobic core, together with His, on the conformational changes in respective peptides designated as HA, HV, HI, and HL, resp...

Valence bond (VB) picture and valence shell electron pair repulsion principle (VSEPR) [1, 2, 3] are localized bond approaches. VB picture is the historic landmark for modern chemistry, which is based on the valence bond. It invests each atom with the valence according to the number of electron, which is the basic concept for chemical bonds of the m...

The vibronic coupling constant (VCC), as well as the vibronic coupling density (VCD), will be exactly defined in this chapter. Before the precise definition of VCC and VCD, we will introduce Dirac’s notation and the basic concept of group and symmetry. The definition of the normal coordinates will be given, and the characters and the direct product...

The vibronic coupling constant (VCC) offers quantitative insight into the molecular design. The diagonal VCC is the gradient of a potential energy surface concerning the normal coordinate at a fixed nuclear configuration as defined in Sect. 5.4.1, which can give the quantitative evaluation of the force which occurred under an electronic transition....

The basis of the vibronic coupling density (VCD) analysis has been introduced in Chap. 2. The vibronic coupling constant (VCC) as well as the VCD will be exactly defined in Sect. 5.4.1. As seen in Sect. 5.4.1, both are starting from the ab initio molecular Hamiltonian, and systematic, rational ways to understand chemical phenomena, and which can gi...

We define a molecular deformation, and discuss how to specify molecular deformations in a diatomic and triatomic molecules A\(_3\) and A\(_2\)B taken as examples. An approximate molecular Hamiltonian for a polyatomic molecule is introduced. The origins of molecular deformations, vibronic couplings, are discussed for non-degenerate electronic states...

This paper describes a new synthetic method of p-conjugated Mobius molecule by inserting an alkene or ortho-phenylene to cycloparaphenylenes. Physical properties of the obtained compounds were also studied.

The termination mechanism in the radical polymerization of acrylonitrile (AN) was determined by the reaction of structurally well-defined polyacryronitrile (PAN) chain-end radical 1a and PAN-end mimetic small model radical 1b . The contributions of three mechanisms, i.e., the disproportionation ( Disp ), the combination by carbon-carbon formation (...

The effect of viscosity on the radical termination reaction between a transient radical and a persistent radical undergoing a coupling reaction (Coup) or hydrogen abstraction (Abst) was examined. In a non-viscous solvent, such as benzene (bulk viscosity ηbulk < 1 mPa s), all the transient radicals studied exclusively coupled with 2,2,6,6-tetramethy...

This book introduces vibronic coupling density and vibronic coupling constant analyses as a way to understand molecular structure and chemical reactions. After quantum study, the behavior of electrons circulating around nuclei led to the principal concept that underlies all explanations in chemistry. Many textbooks have given plausible explanations...

Using pulsed electron paramagnetic resonance (EPR) techniques, the low-temperature magnetic properties of the NO radical being confined in two different modified open C60-derived cages are determined. It is found that the smallest principal g value g3, being assigned to the axis of the radical, deviates strongly from the free electron value. This b...

Abstract. Using pulsed EPR techniques, the low temperature magnetic properties of the NO radical being confined in a C60 derived cage are determined. It is found that the smallest principal g value g ₃, being assigned to the axis of the radical, deviates strongly from the free electron value. This behavior results from partial compensati...

A heterogeneous metal-loaded titanium oxide photocatalyst provided an efficient route to bring out direct dehydrogenative cross-coupling between toluene and acetone without consuming any additional oxidizing agent. The nature of the metal nanoparticle cocatalyst deposited on TiO2 photocatalyst dictated the product selectivity for the cross-coupling...

Commonly, in molecular inclusion phenomena or molecular recognition processes, flexibility on the molecular size or shape of a host molecule is incompatible with a high affinity of association and accuracy of selectivity. However, if the host has a narrow access for incorporating the guest, the transition process during the complexation requires a...

Metal-free magnetic mixed micelles (mean diameter: 16 nm) composed of biocompatible surfactant Tween 80 and hydrophobic pyrrolidine-N-oxyl radical were prepared by mixing them in phosphate-buffered saline. The magnetic mixed micelles were characterized by dynamic light scattering and small angle neutron scattering measurements. The stability of the...

Metal-free magnetic mixed micelles (mean diameter: < 20 nm) were prepared by mixing the biocompatible non-ionic surfactant Tween 80 and the non-toxic, hydrophobic pyrrolidine-N-oxyl radicals bearing a d-glucosamine unit in pH 7.4 phosphate-buffered saline (PBS). The time-course stability and in vitro magnetic resonance imaging (MRI) contrast abilit...

A platinum(II) terpyridine complex having an enantiopure lactate anion afforded hydrated crystals l- or d-1hyd containing infinite chains of interacting Pt centers, while their dehydration induced crystal-to-crystal transformation into l- or d-1dehyd, respectively, exhibiting less significant Pt-Pt and/or ligand-ligand interactions. That transforma...

Endohedral metallofullerenes have been extensively studied since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C60 such as (metal)@C82, and there are no reported purified C60-based monomeric metallofullerenes, except for [Li@C60...

A reactive radical species, nitric oxide (NO), was encapsulated as a unimolecular form inside an open‐cage fullerene derivative under high‐pressure conditions in solid state. Surprisingly, the molecular complex showed sharp 1H NMR signals in spite of existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the...

A reactive radical species, nitric oxide (NO), was encapsulated as a unimolecular form inside an open‐cage fullerene derivative under high‐pressure conditions in solid state. Surprisingly, the molecular complex showed sharp 1H NMR signals in spite of existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the...

Cofacial assemblies of metalloporphyrinoids represent a fascinating platform for the fabrication of novel functional molecular assemblies based on π-π, d-d, and d-π interactions between components. In this paper, we present a novel synthetic strategy for the programmable arrangement of different metal ions inside a cofacially stacked trimer of porp...

Commonly, in molecular inclusion phenomena or molecular recognition processes, flexibility on the molecular size or shape of a host molecule is incompatible with a high affinity of association and accuracy of selectivity. However, if the host has a narrow access for incorporating the guest, the transition process during the complexation requires a...

Endohedral metallofullerenes have been extensively studied, since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, all of these studies have been carried out on metallofullerenes larger than C60 such as (metal)@C82, and there are no reported purified C60-based metallofullerenes except for [Li@C60]+...

Conductive inks that are composed mainly of metal nanoparticles are used as core materials for printed electronics. We developed a production method of new copper complex solutions, which by reductive heating yielded copper nanoparticles dispersion liquids of less than 100 nm in particle diameter. The copper complex solutions are grouped into three...

A contracted doubly N-confused dioxohexaphyrin(1.1.1.1.1.0) complex consisting of two paramagnetic copper metals and open-shell π radical ligand was synthesized as a new multi-heterospin motif. X-ray spectroscopy supported the divalent character of the inner copper centers, and electron paramagnetic resonance and magnetometric studies suggested the...

A multiply interlocked catenane with a novel molecular topology was synthesized; a phthalocyanine bearing four peripheral crown ethers was quadruply interlocked with a cofacial porphyrin dimer bridged with four alkylammonium chains. The supramolecular conjugate has two nanospaces surrounded by a porphyrin, a phthalocyanine, and four alkyl chains to...

A multiply interlocked catenane with a novel molecular topology was synthesized; a phthalocyanine bearing four peripheral crown ethers was quadruply interlocked with a cofacial porphyrin dimer bridged with four alkylammonium chains. The supramolecular conjugate has two nanospaces surrounded by a porphyrin, a phthalocyanine, and four alkyl chains to...

With a view to developing a theranostic nanomedicine for magnetic resonance (MR) imaging-visible targeted drug delivery system, robust metal-free magnetic nanoemulsions (mean particle sizes of less than 20 nm) consisting of the biocompatible surfactant 1 and the incorporated hydrophobic low-molecular-weight 2,2,5-trimethyl-5-(4-alkoxy)phenylpyrroli...

The chapter describes electron spin resonance (ESR) spectroscopic studies of lanthanide endohedral metallofullerenes. A summary of recent investigations of La@C82, La2@C80, and their reduced anion and radical species is presented. Also discussed are ESR studies of lanthanide metallofullerene with high spin state, including Eu@C74, Eu@C82, Gd@C82, a...

The photocatalytic sp³C–sp³C cross-coupling between tetrahydrofuran (THF) and various alkanes was accomplished with Pt loaded titanium oxide (Pt/TiO2) photocatalysts. The cross-coupling between THF and cyclohexane was systematically studied, which revealed that the reaction followed two routes: the main course was the photooxidation of both substra...

To investigate the intrinsic reactivity of atomic nitrogen, which had previously been accomplished only by examining its decay in the gas phase using special equipment, a nitrogen atom was inserted into a series of molecule-encapsulating C60 and C70 fullerenes. Among the studied endofullerenes, H2@C70 was able to encapsulate an additional nitrogen...

To investigate the intrinsic reactivity of atomic nitrogen, which had previously been accomplished only by examining its decay in the gas phase using special equipment, a nitrogen atom was inserted into a series of molecule-encapsulating C60 and C70 fullerenes. Among the studied endofullerenes, H2@C70 was able to encapsulate an additional nitrogen...

A platinum-loaded TiO2 (Pt/TiO2) photocatalyst promoted cyanomethylation of aliphatic hydrocarbons, namely cyclohexane and cyclohexene, with acetonitrile, where the photogenerated hole oxidatively dissociates the C–H bond of both the acetonitrile and the aliphatic hydrocarbons to form each corresponding radical species before their radical cross-co...

A supramolecular complex was constructed by encapsulation of a (3) O2 molecule inside an open-cage C60 derivative. Its single-crystal X-ray diffraction analysis revealed the presence of the (3) O2 at the center of the fullerene cage. The CV measurements suggested that unprecedented dehydrogenation was promoted by the encapsulated (3) O2 after two-e...

A reaction of a ruthenium(ii) NAD-type complex, [Ru(tpy)(pbn)(Cl)](+) (tpy = 2,2':6',2''-terpyridine; pbn = 2-(pyridin-2-yl)benzo[b][1,5]naphthyridine), with pressurized CO (2 MPa) at 150 °C in H2O selectively produced a two-electron reduced ruthenium(ii)-NADH-type carbonyl complex, [Ru(tpy)(pbnHH)(CO)](2+) (pbnHH = 2-(pyridin-2-yl)-5,10-dihydroben...

A supramolecular complex was constructed by encapsulation of a 3O2 molecule inside an open-cage C60 derivative. Its single-crystal X-ray diffraction analysis revealed the presence of the 3O2 at the center of the fullerene cage. The CV measurements suggested that unprecedented dehydrogenation was promoted by the encapsulated 3O2 after two-electron r...

The electronic and molecular structures of 9,10-diamino-substituted anthracenes with different N-substituents have been re-examined. In particular, different N-substituents influence both the electronic and molecular structures of the oxidized species of 9,10-diaminoanthracenes. The anthrylene moiety of 9,10-bis(N,N-di(p-anisyl)amino)anthracene ret...

Self-organization of phthalocyanines has been programmed on a porphyrin template. Two phthalocyanines with four peripheral crown ether units are stacked cofacially on a porphyrin bearing four alkylammonium chains, in accordance with the number of ammonium groups on the side chain, through fourfold rotaxane formation. Significant electronic interact...

A stacked assembly composed of a porphyrin and two phthalocyanines was prepared through fourfold rotaxane formation. Two phthalocyanine molecules, bearing four 24-crown-8 units, were assembled onto a porphyrin template incorporating four sidechains with two dialkylammonium ions each through pseudorotaxane formation between crown ether units and amm...

Lithium-encapsulated [60]fullerene [email protected]60, namely, lithium-ion-encapsulated [60]fullerene radical anion Li⁺@C60⁻, was synthesised by electrochemical reduction of lithium-ion-encapsulated [60]fullerene trifluoromethanesulfonylimide salt [Li⁺@C60](TFSI⁻). The product was fully characterised by UV-vis-NIR absorption and ESR spectroscopy a...

A rational and effective approach for synthesizing linear π-conjugated hexa-, hepta- and octapyrrins through regioselectively oxidative coupling of monoacylated tripyrrane and bilane is described. Dependent upon the numbers of pyrrolic units, the geometry and properties of bis-copper complexes could be systematically modulated.

Endohedral metallofullerenes (EMFs) have novel structures and properties that are closely associated with the internal metallic species. Benzyl radical additions have been previously shown to form closed-shell adducts by attaching an odd number of addends to open-shell EMFs (such as Sc3 C2 @Ih -C80 ) whereas an even number of groups are added to cl...

Palladium loaded titanium oxide was found to work as a bifunctional photocatalyst for functionalization of benzene with ether upon photoirradiation, without using any special reagents. The metal loaded TiO2 photocatalyst activated a C–H bond of ethers and the heterogeneous Pd metal nanoparticle catalyst promoted the successive C–C bond formation be...

Radical cations and dications of [n]cycloparaphenylenes ([n]CPPs, n = 5, 6, 10, and 12), which are the models of those of linear oligoparaphenylenes without a terminus, were synthesized as hexafuloroantimonate salts by the one and two-electron chemical oxidation of CPP by NOSbF6 or SbF6. The radical cations, [n]CPP•+, and dications, [n]CPP2+, exhib...

We present the first report of a compact, planar and low-energy-gap molecule based on a π-conjugated bimetal system comprising a tetrathiooxalate () skeleton. The observed low HOMO-LUMO energy gap (1.19 eV) is attributed to its donor-acceptor-donor (D-A-D) nature because the skeleton acts as an electron acceptor as well as a tiny and noninnocent br...

An optically active amphiphilic nitroxide radical compound [(S,S,R)-5a], which contains a paramagnetic (2S,5S)-2,5-dimethyl-2,5-diphenylpyrrolidine-N-oxyl radical group fixed in the inner position together with a hydrophobic long alkyl chain and a hydrophilic (R)-alanine residue in the opposite terminal positions, was found to serve as a low-molecu...

A contracted doubly N-confused dioxohexaphyrin derivative served as a dinucleating metal ligand for unsymmetrical coordination. The complexation of two palladium(II) cations led to the formation of π-radical species that were persistent in atmospheric air in the presence of moisture. Effective delocalization of an unpaired electron over the hexaphy...

A contracted doubly N-confused dioxohexaphyrin derivative served as a dinucleating metal ligand for unsymmetrical coordination. The complexation of two palladium(II) cations led to the formation of π-radical species that were persistent in atmospheric air in the presence of moisture. Effective delocalization of an unpaired electron over the hexaphy...

Fullerenyl radicals can be generated by addition of a free radical to a fullerene surface, by nucleophilic addition followed by one-electron oxidation, or by thermal dissociation of singly-bonded fullerene dimers. However, fullerenyl radicals are usually very reactive and generally cannot be isolated. On the contrary, we have found that the reactio...

[11]Cycloparaphenylene ([11]CPP) selectively encapsulates La@C82 to form the shortest possible metallofullerene–carbon nanotube (CNT) peapod, La@C82⊂[11]CPP, in solution and in the solid state. Complexation in solution was affected by the polarity of the solvent and was 16 times stronger in the polar solvent nitrobenzene than in the nonpolar solven...

We prepared nanorods for various endohedral fullerenes as a well-arrayed nanostructure using a liquid–liquid interfacial precipitation method and magnetically aligned them under a magnetic field (10–12 T). The nanorod orientation was observed using a microscope or scanning electron microscopy. Nanorod fullerenes examined in this study include prist...

A heterodinuclear complex, syn-[PtCu(μ-pyt)2(bpy)2](2+) (syn-[PtCu]; Hpyt = pyridine-2-thiol, bpy = 2,2'-bipyridine), was synthesized by stepwise complexation. Three different crystal structures of the hexafluorophosphate salts with solvent molecules as guests at the axial sites of the Cu(ii) ions, i.e. syn-[PtCu-G] (G = acetonitrile, acetone, and...

The instability of the cylindrical D6h structure in [6]cycloparaphenylene, the non-zero dihedral angles between adjacent paraphenylene units, is investigated from the viewpoint of the pseudo Jahn-Teller effect, wherein the driving forces are orbital vibronic couplings of the deformation modes between occupied and unoccupied orbitals. We show that t...

Charged nanobelts: The radical cation and the dication of [8]cycloparaphenylene ([8]CPP) were prepared and isolated as hexahaloantimonate salts by the one- or two-electron chemical oxidation of [8]CPP with NOSbF6 or SbCl5 . ESR spectroscopy of CPP(.+) and single-crystal X-ray analysis of CPP(2+) demonstrated that the spin and charge were equally an...

Three kinds of para-phenylenediamine (PDA) derivatives bearing nitronyl nitroxide (NN) groups were prepared and characterized on the basis of the electrochemical, electron spin resonance (ESR) spectroscopic, absorption spectroscopic, and magnetic susceptibility measurements. It was clarified that the oxidation potential of the central PDA unit is s...

Cation radicals of some aromatic hydrocarbons, aliphatic amines, and aromatic amines are produced by γ irradiation of frozen glassy solutions using organic halides as the solvent. The electronic absorption spectra of the cation radicals are compared with the photoelectron spectra of the parent molecules in order to find correlations between the two...

Two kinds of octaazacyclophanes, octaaza[18]m,p,m,p,m,p,m,p- cyclophane 2 and octaaza[18]m,p,p,p,m,p,p,p-cyclophane 3, as ring-size extended congeners of tetraaza[14]m,p,m,p-cyclophane were synthesized, and the electronic states of their polycationic species were investigated by quantum chemical calculations, electrochemical measurements (cyclic vo...

Single crystal X-ray analysis has been used as a powerful method to determine the structure of molecules. However, crystallographic data containing helium has not been reported, owing to the difficulty in embedding helium into crystalline materials. Here we report the X-ray diffraction study of He@C and the clear observation of a single helium atom...

Spin doctor: The polymacrocyclic oligoarylamine in the picture serves as a multispin source owing to its multi-electron redox activity. As a result of its pseudobeltane structure and para-phenylenediamine bridges, the radical cation can convert between two sideslipped structures with a windshield-wiper-like motion. In contrast, the tetraazacyclopha...

Oligoarylamin‐Doppeldecker und ‐Tripeldecker wurden hergestellt und durch Röntgenkristallographie charakterisiert (siehe Bild; C schwarz, N blau). Die N‐Dianisylaminophenyl‐substituierten Doppeldecker gehen mehrere Redoxreaktionen ein, wobei die oxidierten Spezies laut Puls‐ESR‐Spektroskopie in High‐Spin‐Zuständen vorliegen.

Double- and triple-decker oligoarylamines have been prepared and characterized by X-ray crystallography for the first time (see picture; C black, N blue). The N-dianisylaminophenyl-substituted double decker exhibited the multiredox activity, and the oxidized species were confirmed to be in high-spin states on the basis of pulsed ESR spectroscopy.

C60 nanowhiskers (NWs) containing N@C60 were prepared by a liquid–liquid interfacial precipitation method. The ESR spectra of N@C60/C60 NWs showed broader lines than N@C60/C60 powder indicating that N@C60 acts as a non-destructive structural probe for fullerene nanomaterials.

The endohedral metallofullerenes, such as Sc@C82, Sc2@C84, and Sc3@C82, have been purified and isolated by using two-stage high-performance liquid chromatography (HPLC). The ESR spectrum of the isolated Sc3@C82 exhibits a perfectly symmetric 22 hyperfined splittings with an inherent linewidth of 0.77 Gauss at 220 K, which is consistent with a uniqu...

Firmly tied: A four-fold rotaxane was prepared from a porphyrin unit with four alkylammonium chains and a phthalocyanine unit with four peripheral crown ethers. In a dinuclear Cu(2+) complex of the four-fold rotaxane, the Cu(2+) -porphyrin and the Cu(2+) -phthalocyanine moieties were stacked efficiently on one another to afford spin-spin communicat...

The complexation behavior of La(2)@C(80) dimetallofullerenes with organic donor molecules (D) in solution has been investigated. It has been shown that La(2)@C(80) and D form 1:1 complexes as a result of electron transfer interactions in the ground state. The equilibrium between La(2)@C(80)/D and [La(2)@C(80)](•-)/[D](+) in solution is readily cont...

The dimetallic endohedral heterofullerene (EHF), Gd(2)@C(79)N, was prepared and isolated in a relatively high yield when compared with the earlier reported heterofullerene, Y(2)@C(79)N. Computational (DFT), chemical reactivity, Raman, and electrochemical studies all suggest that the purified Gd(2)@C(79)N, with the heterofullerene cage, (C(79)N)(5-)...

The cyclic host cyclo-[P(Cu)](2) carrying two covalently connected Cu(II) porphyrin units can accommodate La@C(82), a paramagnetic endohedral metallofullerene, in its cavity to form the inclusion complex cyclo-[P(Cu)](2)⊃La@C(82), which can be transformed into the caged complex cage-[P(Cu)](2)⊃La@C(82) by ring-closing olefin metathesis of its side-...

Hydrogen-end-capped polyynes, H(C≡C)(n)H (n = 5-7), were photoirradiated in the presence of iodine molecules in nonpolar solvents to find a dramatic change in the UV/vis absorption spectrum. Absorption bands of polyynes in the UV and the band of I(2) in the visible region disappeared, whereas weaker bands of polyynes were intensified in the near UV...

Although chordoma, a rare bone cancer, has been treated with surgery and/or radiation including heavy ions, few in vitro characterizations of chordoma cells are available. The main reason for this is the extremely long doubling time associated with the only recognized cell line, U-CH1. Here, we derived a cell line (designated as U-CH1-N) from U-CH1...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Retro-reaction of radical monoadducts of a paramagnetic endohedral metallofullerene, La@C(2v)-C(82), is shown using thermal reaction in the presence of a radical trapping reagent, affording pristine La@C(2v)-C(82) in high yield (96%).

para-Phenylene-bridged spirobi(triarylamine) dimer 2, in which π conjugation through four redox-active triarylamine subunits is partially segregated by the unique perpendicular conformation, was prepared and characterized by structural, electrochemical, and spectroscopic methods. Quantum chemical calculations (DFT and CASSCF) predicted that the fro...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Addition reaction of an endohedral metallofullerene La@C-82 with digermirane has been investigated by means of the mass and EPR measurements. It is found that photochemical and thermal reactions of La@C-82 with digermirane afford an exohedral adduct of the endohedral metallofullerene. This is in sharp contrast with the fact that empty fullerenes re...

The line widths of the hyperfine components of ESR spectra of La C82 and Sc C82 in CS2 and toluene solutions have been measured as a function of temperature. The extent of line broadening due not only to the insufficient rotational averaging of g and hyperfine tensors but also to the spin-rotation coupling interaction have been determined. The valu...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The first regioselective functionalization of La@C(82) by two different groups has been performed. Bis-adducts of La@C(82) with Cp* and adamantylidene were synthesized by using two different routes and characterized. Spectroscopic analysis and theoretical calculations reveal that the addition position is controlled by the charge density and p-orbit...

We herein report the investigation of N@C(60) exposed to laser flash excitation to exhibit the acceleration of the decay of (N@C(60))* by the encased N atom.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The two regioisomers of endohedral pyrrolidinodimetallofullerenes M(2)@I(h)-C(80)(CH(2))(2)NTrt (M = La, Ce; Trt = trityl) were synthesized, isolated, and characterized. X-ray crystallographic analyses of [6,6]-La(2)@I(h)-C(80)(CH(2))(2)NTrt and [6,6]-Ce(2)@I(h)-C(80)(CH(2))(2)NTrt revealed that the encapsulated metal atoms are located at the slant...

High-spin alignment for dicationic, tricationic, tetracationic and hexacationic species of a meta-para-linked oligoarylamine was accomplished by incorporating cyclophane skeletons into the oligomer backbone.

Polycations of two oligoanilines based on Wurster's blue,N,N′,N″-tris[4-(dimethylamino)phenyl]-N,N′,N″-trimethyl-1,3,5-benzenetriamine (2) and N,N′-bis(3-{N-[4-(dimethylamino)phenyl]-N-methylamino}phenyl)-N,N′-dimethyl-p-phenylenediamine (3), have been generated efficiently by a stepwise oxidation procedure. Their redox behavior was characterized i...

Derivatives of Ce@C(82)(C(2v)) have been synthesized and fully characterized, and their anisotropic magnetism has been observed as paramagnetic shifts in NMR measurements. Carbene addition by photochemical reaction afforded two isomers of Ce@C(82)(C(2v))Ad (Ad = adamantylidene), 2a and 2b, demonstrating high regioselectivity. The two isomers were c...

Encapsulation by synthetic hosts can transform the spin states of square planar Ni(II)(acen) and Co(II)(tap) complexes. Upon encapsulation, the red Ni(II) diamagnetic state was converted into a green paramagnetic state, whereas the Co(II) low spin (S = 1/2) state was changed into a coupled (S = 1/2 and S = 3/2) state. The host cages are noninnocent...