Investigation of Various Organic Radicals Dispersed in Polymethylmethacrylate Matrices Using the Electron Spin Resonance Spectroscopy Technique.

The electron spin resonance (ESR) spectroscopy technique was used to study various organic radicals, such as 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO), 4-hydroxy-TEMPO (TEMPOL), 2-X-nitronylnitroxide (2-X-NN, X = Ph, NO2Ph, or cyclohexyl), 4-Y-benzonitronylnitroxide (4-Y-PhBzNN, Y = Ph or NO2Ph), and 2-Z-iminonitroxide (2-Z-IN, Z = Ph or NO2Ph) dispersed in a polymethylmethacrylate (PMMA) matrix. The experiments were conducted at room temperature. The complex nature of the recorded ESR spectra could be attributed to the superposition of the rotational diffusion component of TEMPO (or TEMPOL) in the nanospace of the PMMA matrix with the rigid-limit component. A single component of the rigid-limit was observed for 2-X-NN and 4-Y-PhBzNN radicals dispersed in the PMMA matrix. The isotropic components of g and hyperfine ( A ) tensor, estimated by analyzing the solution spectra, were used to determine the g and A components of 4-Y-PhBzNN. Only the rotational diffusion component was observed for the 2-Z-IN radical. These results demonstrated that the PMMA matrix contains cylindrical nanospaces. Various radicals other than TEMPO derivatives could be used in the ESR spin probe technique as probe molecules for determining the structures, sizes, and shapes of the nanospaces.

Electron Spin Resonance Study of Molecular Orientation and Dynamics of Phenyl Imino and Nitronyl Nitroxide Radicals in Organic 1D Nanochannels of Tris( o-phenylenedioxy)cyclotriphosphazene.

Imino and nitronyl nitroxide (IN and NN, respectively) radicals such as phenyliminonitroxide (PhIN) and phenylnitronylnitroxide (PhNN), respectively, were dispersed in the organic 1D nanochannels of tris( o-phenylenedioxy)cyclotriphosphazene (TPP). Electron spin resonance (ESR) measurements were conducted on these inclusion compounds (ICs) in the temperature range 4.2-300 K. The modulated-septet ESR spectra of TPP ICs using PhIN observed in the range 165-258 K were reproduced with the EasySpin program package using a model in which some of the PhIN molecules underwent uniaxial rotational diffusion in the TPP nanochannels around the molecular long axis corresponding to the principal y-axis of the g tensor. However, for the TPP IC using PhNN, complicated ESR spectra were observed, which were not consistent with the modulated quintet observed in solution or in the fast-motion limit in solids. These spectra were reproduced by the superposition of a quintet originating from rotational diffusion of PhNN molecules and a septet based on rotational diffusion of PhIN molecules generated in the synthetic process. The rotational diffusion activation energies of PhIN and PhNN in the TPP nanochannels were estimated to be 19 and 45 kJ mol-1 using an Arrhenius plot, respectively. These were consistent with that for NN radicals in the 1D nanochannels of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) (37-54 kJ mol-1) with a larger pore diameter than TPP reported in our previous study, or with that for 4-substituted-2,2,6,6-tetramethyl-1-piperidinyloxyl (4-X-TEMPO) in TPP nanochannels (5-26 kJ mol-1) with regard to molecular size or host-guest or guest-guest interactions. These results indicate that not only the NN group but also IN may be used for the clarification of chemical or biological structures of nanomaterials such as nanosized cavities.

Synthesis, crystal structure and magnetic properties of o-carboranyl nitronyl nitroxide biradical: a prototype of a three-dimensional analogue of o-benzoquinodimethane.

We have designed and synthesised a new carborane derivative containing two nitronyl nitroxides. This molecule can be considered as a prototype of a three-dimensional analogue of o-benzoquinodimethane. The magnetic susceptibility of a crystalline sample revealed that this biradical possesses a weak antiferromagnetic interaction (theta = -1.05(4) K) and an ESR study in frozen matrix in the 5.4-104 K range gave an intramolecular antiferromagnetic interaction of -27(2) K. The synthesis, physical properties and DFT calculation result are also reported.

Synthesis and photochemical properties of a photochromic iron(II) complex of hexaarylbiimidazole.

The photochromic ligand bis(terpyridyl)hexaarylbiimidazole (bistpy-HABI) and the Fe(II) complex of bistpy-HABI with formula [{Fe(tpy)}2.bistpy-HABI](PF6)4.4H2O were synthesized and characterized. Bistpy-HABI is readily cleaved into a pair of terpyridyltriphenylimidazolyl radicals (tpy-TPI*) on irradiation with UV light. This photochemical reaction is completely reversible, and the light-induced radicals can thermally recombine to form bistpy-HABI in the dark. [{Fe(tpy)}2.bistpy-HABI]4+ is the first example of a transition-metal complex of an HABI derivative and was found to show photochromic reaction in solution. The spin state of the light-induced radical pair in a frozen matrix was investigated by ESR spectroscopy. The triplet state of the light-induced radical pair from [{Fe(tpy)}2.bistpy-HABI]4+, as well as that from bistpy-HABI, was confirmed to be a ground state or nearly degenerated with a singlet state. Kinetic studies on the radical recombination reaction in solution elucidated the decrease in the activation energy by forming the Fe(II) complex. This is the first observation of a decrease in the activation energy of the radical recombination reaction by the formation of a metal-coordinated radical complex. The syntheses, photochemical properties, and spin states of bistpy-HABI and [{Fe(tpy)}2.bistpy-HABI](PF6)4 are discussed.

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework.

A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.

Definitive evidence for the contribution of biradical character in a closed-shell molecule, derivative of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene.

This study provides conclusive proof that the thermally excited open-shell state with biradical character is contributing to the ground state of a closed-shell molecule, tF-BDPI-2Y, where four hydrogen atoms at the central phenylene ring are substituted with four fluorine atoms of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene (BDPI-2Y). A small increase in the population of biradical species of tF-BDPI-2Y results in the formation of the dimer form by the radical recombination reaction. Controlling the equilibrium between a closed-shell diamagnetic-quinoid state and an open-shell paramagnetic-biradical state will provide significant progress in the field of pi-conjugated delocalized biradical chemistry.

Carrier doping effect into quasi-one-dimensional bromo-bridged Ni(III) complexes with strong electron-correlation by Cu(II) ions, [Ni1-xCux(chxn)2Br]Br2-x.

This communication will describe the electron doping effect into Ni(III) complexes by Cu(II) ions, [Ni(1-x)Cu(x)(chxn)(2)Br]Br(2-x) (x = 0.038 and 0.101) by using an electrochemical oxidation method. A drastic increase of electrical conductivity as well as a new absorption band around 0.5 eV in single crystal reflectance spectra was observed by doping Cu(II) ions, indicating the electron doping was successfully made. An ESR result shows unpaired electrons locate in the d(x2-y2) orbitals of Cu(II) and have almost no interaction with those of other ions.

Novel ET-coordinated copper(I) complexes: syntheses, structures, and physical properties (ET = BEDT-TTF = Bis(ethylenedithio)tetrathiafulvalene).

New molecular charge-transfer complexes of bis(ethylenedithio)tetrathiafulvalene (ET), (ET)Cu(2)Br(4) (1), (ET)(2)Cu(6)Br(10) (2), (ET)(2)[Cu(4)Br(6)ET] (3), (ET)(2)Cu(2)Br(4) (4), (ET)(2)Cu(3)Br(7)(H(2)O) (5), and (ET)(2)Cu(6)Br(10)(H(2)O)(2) (6), have been synthesized by diffusing reaction of ET and Cu(II)Br(2). Their crystal structures and physical properties have been investigated. X-ray analyses revealed that ET molecules coordinated to the copper ions with the sulfur atoms of the ethylenedithio groups in all compounds. The Cu-S distances are found in the range 2.268(5)-2.417(8) A, being close to the typical Cu(I)-S coordination bond distances. Strong d-pi interactions between d-electrons of the copper ions and pi-electrons of the ET molecules can be expected through the Cu-S coordination bonds. ET molecules behave as trans-bidentate ligands bonding to two different copper ions in 1 and 3, as cis-bidentate ligands in 2, 5, and 6, and as monodentate ligands in 4. In the crystal structure of 3, there are two types of ET molecules in the crystal structure, where the first type is a trans-bidentate ligand and the second forms a stacking structure by itself. Compounds 1, 2, 4, and 6 show semiconducting behavior down to low temperature (sigma(RT) = 1.6 x 10(-2) S cm(-1) and E(a) = 122 meV for 1, sigma(RT) = 2.1 S cm(-1) and E(a) = 21 meV for 2, sigma(RT) = 5.4 x 10(-4) S cm(-1) and E(a) = 239 meV for 4, and sigma(RT) = 5.1 x 10(-2) S cm(-1) and E(a) = 207 meV for 6). On the other hand, in 3, a metal-like region is observed along the b-axis and c-axis, due to the contribution of stacked ET molecules, and a metal-semiconductor transition occurs at 280 and 270 K, respectively. Also, 5 exhibits metallic conductivity in the temperature ranges 240-300 and 200-300 K along the b-axis and c-axis, respectively, despite the oxidation state of ET with 2+.

Heterometallic hexanuclear cluster with an S = 8 spin ground state: MnII[MnII(hfac)2]3[NiII(pao)3]2 (hfac- = hexafluoroacetylacetonate, pao- = pyridine-2-aldoximate).

The heterometallic Mn(II)(4)Ni(II)(2) title compound has been synthesized and characterized by X-ray crystallography. The compound consists of a Ni-Mn-Ni linear moiety, [[Ni-(mu-NO)(3)](2)-Mn], linked by oximate bridges and three Mn(II) hfac terminal units attached by oximate oxygens in a di-mu-oxo fashion, forming a novel heterometallic cluster: Mn[Mn(hfac)(2)](3)[Ni(pao)(3)](2) (1). Magnetic measurements reveal the antiferromagnetic nature of the oximate pathway between Mn(II) and Ni(II) metal ions, which imposes an unusual high-spin ground state (S = 8) for 1.

Tuning of spin density wave strengths in quasi-one-dimensional mixed-halogen-bridged nickel(III) complexes with strong electron correlation, [Ni(III)(chxn)(2)Cl(1-x)Br(x)](NO(3))(2).

This communication describes the syntheses of the quasi-one-dimensional mixed-halogen-bridged Ni(III) complexes with strong electron correlation [Ni(chxn)(2)Cl(1-x)Br(x)](NO(3))(2) and the tuning of the spin density wave strengths of these compounds. If the Cl 3p and Br 4p make one band in the compounds, we should observe a single peak in the electronic spectra. As a result, we should observe the single peak from 1.45 to 2.00 eV depending on the mixing ratios of Cl and Br ions. Therefore, the Cl 3p and Br 4p make one band. Then, we have succeeded in tuning the spin density wave strengths of the Ni(III) complexes with the strong electron correlation by mixing the bridging halogen ions successively.