An n-type semiconducting diazaporphyrin-based hydrogen-bonded organic framework.

Significant effort has been devoted to the development of materials that combine high electrical conductivity and permanent porosity. This paper discloses a diazaporphyrin-based hydrogen-bonded organic framework (HOF) with porosity and n-type semiconductivity. A 5,15-diazaporphyrin Ni(ii) complex with carboxyphenyl groups at the meso positions afforded a HOF due to hydrogen-bonding interactions between the carboxy groups and meso-nitrogen atoms. The thermal and chemical stabilities of the HOF were examined using powder X-ray diffraction analysis, and the charge-carrier mobility was determined to be 2.0 × 10-7 m2 V-1 s-1 using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method. An analogous diazaporphyrin, which does not form a HOF, exhibited mobility that was 20 times lower. The results presented herein highlight the crucial role of hydrogen-bonding networks in achieving conductive pathways that can tolerate thermal perturbation.

Pressure-tuned quantum criticality in the large-D antiferromagnet DTN.

Strongly correlated spin systems can be driven to quantum critical points via various routes. In particular, gapped quantum antiferromagnets can undergo phase transitions into a magnetically ordered state with applied pressure or magnetic field, acting as tuning parameters. These transitions are characterized by z = 1 or z = 2 dynamical critical exponents, determined by the linear and quadratic low-energy dispersion of spin excitations, respectively. Employing high-frequency susceptibility and ultrasound techniques, we demonstrate that the tetragonal easy-plane quantum antiferromagnet NiCl2 ⋅ 4SC(NH2)2 (aka DTN) undergoes a spin-gap closure transition at about 4.2 kbar, resulting in a pressure-induced magnetic ordering. The studies are complemented by high-pressure-electron spin-resonance measurements confirming the proposed scenario. Powder neutron diffraction measurements revealed that no lattice distortion occurs at this pressure and the high spin symmetry is preserved, establishing DTN as a perfect platform to investigate z = 1 quantum critical phenomena. The experimental observations are supported by DMRG calculations, allowing us to quantitatively describe the pressure-driven evolution of critical fields and spin-Hamiltonian parameters in DTN.

Metallaantiaromaticity of 10-Platinacorrole Complexes.

The aromaticity of cyclic π-conjugated organometallic compounds is known as metallaaromaticity. π-Conjugated metallacycles, such as metallabenzenes and metallapentalenes, have been investigated in order to understand the involvement of the d electrons from the metal center in the π-conjugated systems of the organic ligands. Here, we report the synthesis of Pd(II) 10-platinacorrole complexes with cyclooctadiene (COD) and norbornadiene (NBD) ligands. While the Pd(II) 10-platinacorrole COD complex adopts a distorted structure without showing appreciable antiaromaticity, the corresponding NBD complex exhibits a distinct antiaromatic character due to its highly planar conformation. Detailed density functional theory (DFT) calculations revealed that two d orbitals are involved in macrocyclic π-conjugation. We furthermore demonstrated that Craig-Möbius antiaromaticity is not present in the studied system. The synthesis of 10-platinacorroles enables a systematic comparison of the antiaromaticity and aromaticity of closely related porphyrin analogues, providing a better understanding of π-conjugation that involves d orbitals.

Easily Switchable 18π-, 19π-, and 20π-Conjugation of Diazaporphyrin Double-Pincer Bispalladium Complexes.

NiII 3,7,13,17-tetrapyridyl-5,15-diazaporphyrin serves as a double tridentate ligand to PdII ions to provide a pincer-type bispalladium complex. Electrochemical analysis revealed that the bispalladium complex shows excellent ability to accept electrons and reversible redox properties due to the coordination of the two cationic PdII centers to the meso-nitrogen atoms. We isolated and characterized one- and two-electron reduction species of the bispalladium complex. The 20π antiaromatic nature of the two-electron reduction species was confirmed by 1 H NMR spectroscopy, UV/Vis-near-IR (NIR) absorption spectra, and density functional theory (DFT) calculations. X-ray diffraction revealed highly twisted structures for the bispalladium complexes regardless of the oxidation state.

Field-angle-dependent multi-frequency electron spin resonance spectroscopy in submillimeter wave range based on thermal detection.

We report the thermally detected electron spin resonance (ESR) spectroscopy in the frequency range of millimeter and submillimeter waves. Under high vacuum conditions, a cantilever-shaped device detects ESR absorption of a mounted sample as a temperature difference in its beam direction. Despite the simple experimental setup, the spin sensitivity of the order of 1012 spins/G was achieved at 10 K. The developed sample stage is small enough to be used in a 10 T split-pair superconducting magnet with a bore of 25 mm, enabling precise field-angle-dependent ESR measurements at multi-frequencies above 500 GHz. We demonstrate its usefulness by studying the field-angle dependence of the excitation energy of the dimer triplet state in the Shastry-Sutherland magnet SrCu2(BO3)2.

Spin-Crossover-Triggered Linkage Isomerization by the Pedal-like Motion of the Azobenzene Ligand in a Neutral Heteroleptic Iron(III) Complex.

The temperature dependence of magnetic susceptibility of [FeIII(azp)(qsal-Me)]·0.5CH3OH [Hqsal-Me = 5-methyl-N-(8-quinoyl)salicylaldimine, H2azp = 2,2'-azobisphenol] demonstrated that the spin-crossover (SCO) transition behavior changed from an abrupt transition to consecutive gradual conversions, and moreover, the initial abrupt transition was recovered, keeping the complex at room temperature. The variable-temperature crystal structures revealed that an SCO-triggered linkage isomerization of the azobenzene ligand from one orientation to two disordered orientations and the relaxation from the disordered orientations to the original orientation occurred. The high-spin to low-spin relaxation kinetics and theoretical calculation indicate that the pedal-like motion of the azobenzene ligand can be on in the high-spin state whereas off in the low-spin state.

Continuous control of classical-quantum crossover by external high pressure in the coupled chain compound CsCuCl3.

In solid materials, the parameters relevant to quantum effects, such as the spin quantum number, are basically determined and fixed at the chemical synthesis, which makes it challenging to control the amount of quantum correlations. We propose and demonstrate a method for active control of the classical-quantum crossover in magnetic insulators by applying external pressure. As a concrete example, we perform high-field, high-pressure measurements on CsCuCl3, which has the structure of weakly-coupled spin chains. The magnetization process experiences a continuous evolution from the semi-classical realm to the highly-quantum regime with increasing pressure. Based on the idea of "squashing" the spin chains onto a plane, we characterize the change in the quantum correlations by the change in the value of the local spin quantum number of an effective two-dimensional model. This opens a way to access the tunable classical-quantum crossover of two-dimensional spin systems by using alternative systems of coupled-chain compounds.

Iron hexamesityl-5,15-diazaporphyrin: synthesis, structure and catalytic use for direct oxidation of sp3 C-H bonds.

Iron hexamesityl-5,15-diazaporphyrin was synthesized through the cross-coupling reaction of tetrabromodiazaporphyrin. The use of chloroiron(iii) hexamesityl-5,15-diazaporphyrin as a catalyst for oxidation of cyclooctane showed high performance with a total TON up to 731. The introduction of bulky mesityl groups at ß-positions prevented the catalyst deactivation via formation of a µ-oxo dimer.

Synthesis and Characterization of 16π Antiaromatic 2,7-Dihydrodiazapyrenes: Antiaromatic Polycyclic Hydrocarbons with Embedded Nitrogen.

We describe the two-electron reduction of N,N'-dimethyl-2,7-diazapyrenium dications (MDAP2+ ), which afforded the corresponding reduced form (MDAP0 ) as a highly electron-rich 16π antiaromatic system. A single-crystal X-ray diffraction analysis of MDAP0 revealed a distorted quinoidal structure with high bond-length alternation. The 1 H NMR spectrum of MDAP0 exhibited a diagnostic proton signal (4.6 ppm) that is distinctly upfield shifted compared to that of aromatic diazapyrene (8.3 ppm). Theoretical calculations supported the existence of a paratropic ring current. These results indicate that MDAP0 exhibits antiaromatic character derived from its peripheral 16π-electron conjugation.

Peripherally Arylated 2,8-Diazaperylenes from Anthracene Diimide: Synthesis and Oxidative Annulation.

We have synthesized 1,3,7,9-tetrapivaloxy-2,8-diazaperylene through reductive aromatization of anthracene diimide in the presence of zinc powder and pivalic anhydride. The pivaloxy groups were readily converted to aryl groups through nickel-catalyzed cross-coupling reaction with arylboronic acids. Introduction of the nitrogen atoms imparts acid responsiveness to the perylene skeleton, resulting significant changes in its photophysical properties. Oxidative annulation of the peripheral aryl groups with bay positions of the diazaperylene core provided 2,10-diazadibenzocoronenes in good yields.

The Impact of the Next-Nearest Neighbor Dispersion Interactions on Spin Crossover Transition Enthalpy Evidenced by Experimental and Computational Analyses of Neutral π-Extended Heteroleptic Fe(III) Complexes.

A neutral heteroleptic Fe(III) complex 1 derived from a π-extension of the parent complex 2 was prepared and characterized. Complex 1 exhibited an abrupt spin crossover (SCO) transition exactly at room temperature (TSCO = 298 K). A crystal structure analysis of 1 revealed that the Fe(III) complex molecules formed a three-dimensional π-stacking interaction network. To thermodynamically clarify the mechanism of the SCO transition, the thermodynamic parameters of the SCO transitions for 1 and 2 were deduced from the temperature dependence of the magnetic susceptibility in the solid and solution states using the regular solution model. A comparison of the SCO enthalpy difference between the solid and molecule for 1 and 2 revealed that the lattice enthalpy difference would largely contribute to the SCO transition enthalpy difference. A computational evaluation of intermolecular interactions and lattice energies before and after the SCO transitions in 1 and 2 disclosed the significant contribution of the next-nearest neighbor dispersion interactions to the lattice enthalpy differences. This finding indicates that not only conventional nearest neighbor intermolecular interactions but also next-nearest neighbor dispersion interactions should be taken into account to understand the fundamental mechanism of a phase transition in molecular solids.

Helimagnetic Structure and Heavy-Fermion-Like Behavior in the Vicinity of the Quantum Critical Point in Mn_{3}P.

Antiferromagnet Mn_{3}P with Neel temperature T_{N}=30 K is composed of Mn tetrahedrons and zigzag chains formed by three inequivalent Mn sites. Due to the nearly frustrated lattice with many short Mn-Mn bonds, competition of the exchange interactions is expected. We here investigate the magnetic structure and physical properties including pressure effect in single crystals of this material, and reveal a complex yet well-ordered helimagnetic structure. The itinerant character of this materials is strong, and the ordered state with small magnetic moments is easily suppressed under pressure, exhibiting a quantum critical point at ∼1.6 GPa. The remarkable mass renormalization, even in the ordered state, and an incoherent-coherent crossover in the low-temperature region, characterize an unusual electronic state in Mn_{3}P, which is most likely effected by the underlying frustration effect.

Pressure Effect on Zero-Field Splitting Parameter of Hemin: Model Case of Hemoproteins under Pressure.

We experimentally studied the pressure dependence of the zero-field splitting (ZFS) parameter of hemin (iron(III) protoporphyrin IX chloride), which is a model complex of hemoproteins, via high-frequency and high-field electron paramagnetic resonance (HFEPR) under pressure. Owing to the large ZFS, the pressure effect on the electronic structure of iron-porphyrin complexes has not yet been explored using EPR. Therefore, we systematically studied this effect using our newly developed sub-terahertz EPR spectroscopy system in the frequency range of 80-515 GHz, under magnetic fields up to 10 T and pressure up to 2 GPa. We observed a systematic shift of the resonance fields of hemin upon pressure application, from which the axial component of the ZFS parameter was found to increase from D = 6.9 to 7.9 cm-1 at 2 GPa. In contrast to the previous methods used to study proteins under pressure, which mainly focused on conformational changes, our HFEPR technique can obtain more microscopic insights into the electronic structures of metal ions under pressure. In this sense, our technique provides novel opportunities to study the pressure effects on biofunctional active centers of versatile metalloproteins.

Contribution of Coulomb Interactions to a Two-Step Crystal Structure Phase Transformation Coupled with a Significant Change in Spin Crossover Behavior for a Series of Charged FeII Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine.

A series of [FeII(L)2](BF4)2 compounds were structurally and physically characterized (L = 2,6-bis(2-methylthiazol-4-yl)pyridine). A crystal structure phase transformation from dihydrate compound 1 to anhydrous compound 3 through partially hydrated compounds 2 and 2' upon dehydration was found. Compounds 1 and 3 exhibited a gradual spin crossover (SCO) conversion, whereas compounds 2 and 2' demonstrated two-step and one-step abrupt SCO transitions, respectively. An X-ray single-crystal structural analysis revealed that one-dimensional and two-dimensional Fe cation networks linked by π stacking and sulfur-sulfur interactions were formed in 1 and 3, respectively. A thermodynamic analysis of the magnetic susceptibility for 1, 2', and 3 suggests that the enthalpy differences may govern SCO transition behaviors in the polymorphic compounds 2' and 3. A structural comparison between 1 and 3 indicates that the SCO behavior variations and crystal structure transformation in the present [FeII(L)2](BF4)2 compounds can be interpreted by the relationship between the lattice enthalpies mainly arising from Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals.

Paramagnetic ionic plastic crystals containing the octamethylferrocenium cation: counteranion dependence of phase transitions and crystal structures.

In recent years, ionic plastic crystals have attracted much attention. Many metallocenium salts exhibit plastic phases, but factors affecting their phase transitions are yet to be elucidated. To investigate these factors, we synthesized octamethylferrocenium salts with various counteranions [Fe(C5Me4H)2]X ([1]X; X- = B(CN)4-, C(CN)3-, N(CN)2-, FSA (= (SO2F)2N-), FeCl4-, GaCl4- and CPFSA (= CF2(SO2CF2)2N-)) and elucidated their crystal structures and phase behavior. Correlations between the crystal structures and phase sequences, and the shapes and volumes of the anions are discussed. Except for [1][CPFSA], these salts exhibit phase transitions to plastic phases at or above room temperature (TC = 298-386 K), and the plastic phases exhibit either NaCl- or anti-NiAs-type structures. X-ray crystal structure analyses of these salts at 100 K revealed that they have structures in which cations and anions are alternately arranged, with the exception of [1][CPFSA]. [1][CPFSA] exhibits a structure in which anions and cations are separately stacked to form columns. [1][N(CN)2] exhibits a polar crystal structure that undergoes a monotropic phase transition to a centrosymmetric structure. The magnetic susceptibilities of room-temperature plastic crystals [1][GaCl4] and [1][FeCl4] were investigated; the latter exhibits a small ferromagnetic interaction at low temperatures.

Electron magnetic resonance data on high-spin Mn(III; S=2) ions in porphyrinic and salen complexes modeled by microscopic spin Hamiltonian approach.

The spin Hamiltonian (SH) parameters experimentally determined by EMR (EPR) may be corroborated or otherwise using various theoretical modeling approaches. To this end semiempirical modeling is carried out for high-spin (S=2) manganese (III) 3d4 ions in complex of tetraphenylporphyrinato manganese (III) chloride (MnTPPCl). This modeling utilizes the microscopic spin Hamiltonians (MSH) approach developed for the 3d4 and 3d6 ions with spin S=2 at orthorhombic and tetragonal symmetry sites in crystals, which exhibit an orbital singlet ground state. Calculations of the zero-field splitting (ZFS) parameters and the Zeeman electronic (Ze) factors (g||=gz, g⊥=gx=gy) are carried out for wide ranges of values of the microscopic parameters using the MSH/VBA package. This enables to examine the dependence of the theoretically determined ZFS parameters bkq (in the Stevens notation) and the Zeeman factors gi on the spin-orbit (λ), spin-spin (ρ) coupling constant, and the ligand-field energy levels (Δi) within the 5D multiplet. The results are presented in suitable tables and graphs. The values of λ, ρ, and Δi best describing Mn(III) ions in MnTPPCl are determined by matching the theoretical second-rank ZFSP b20(D) parameter and the experimental one. The fourth-rank ZFS parameters (b40, b44) and the ρ (spin-spin)-related contributions, which have been omitted in previous studies, are considered for the first time here and are found important. Semiempirical modeling results are compared with those obtained recently by the density functional theory (DFT) and/or ab initio methods.

Cooperative spin-crossover transition from three-dimensional purely π-stacking interactions in a neutral heteroleptic azobisphenolate FeIII complex with a N3O3 coordination sphere.

A novel neutral heteroleptic FeIII complex from two kinds of π-extended tridentate ligands was designed and prepared. The π-ligands formed a three-dimensional purely π-stacking interaction network. The present complex proved to be the first neutral spin-crossover (SCO) FeIII complex with a N3O3 coordination sphere exhibiting an abrupt SCO transition with a thermal hysteresis of 10 K and the light-induced excited spin-state trapping effect.

Thermochromic Magnetic Ionic Liquids from Cationic Nickel(II) Complexes Exhibiting Intramolecular Coordination Equilibrium.

Among the various thermochromic materials, liquid thermochromic materials are comparatively rare. To produce functional thermochromic liquids, we have designed ionic liquids based on cationic nickel complexes with ether side chains, [Ni(acac)(Me2 NC2 H4 NR1 R2 )]Tf2 N ([1]Tf2 N: R1 =C3 H6 OEt, R2 =Me; [2]Tf2 N: R1 =C3 H6 OMe, R2 =Me; [3]Tf2 N: R1 =R2 =C3 H6 OMe), where acac=acetylacetonate and Tf2 N=(F3 CSO2 )2 N- . The side chains (R1 , R2 ) can moderately coordinate to the metal center, enabling temperature-dependent coordination equilibria in the liquid state. [1]Tf2 N is a liquid at room temperature. [2]Tf2 N is obtained as a solid (Tm =352.7 K) but remains liquid at room temperature after melting. [3]Tf2 N is a solid with a high melting point (Tm =422.3 K). These salts display thermochromism in the liquid state, appearing red at high temperatures and orange, light-blue, or bluish-green at lower temperatures, and exhibiting concomitant changes in their magnetic properties. This phenomenon is based on temperature-dependent equilibrium between a square-planar diamagnetic species and a paramagnetic species with intramolecular ether coordination.

Oxalate-bridged heterometallic chains with monocationic dabco derivatives.

A series of bimetallic oxalate-bridged one-dimensional chains with monocationic dabco derivatives, ({R-dabco}[M(solv)2][Cr(ox)3]·n(solv)) (dabco = 1,4-diazabicyclo[2.2.2]octane, H2ox = oxalate; R = H, M = Co (1); R = H, M = Zn (2); R = Bu, M = Co (3); R = Bu, M = Zn (4)) were synthesized. All compounds have one-dimensional zig-zag chain structures with R-dabco cations located between chains. Cryomagnetic studies reveal that 1 and 3 showed intrachain ferromagnetic interactions between Co(ii) and Cr(iii) ions and metamagnetic behaviour due to interchain antiferromagnetic interactions. Permittivity measurements on compound 4 indicate specific paraelectronic relaxation behaviour originating from the rotational motion of the dabco alkyl substituent.

A New Family of Anionic Fe(III) Spin Crossover Complexes Featuring a Weak-Field N2O4 Coordination Octahedron.

Unprecedented anionic Fe(III) spin crossover (SCO) complexes involving a weak-field O,N,O-tridentate ligand were discovered. The SCO transition was evidenced by the temperature variations in magnetic susceptibility, Mössbauer spectrum, and coordination structure. The DFT calculations suggested that larger coefficients on the azo group in the HOMO-1 of a ligand might contribute to the enhancement of a ligand-field splitting energy. The present anionic SCO complex also exhibited the light- induced excited-spin-state trapping effect.