Large-Amplitude Thermal Vibration-Coupled Valence Tautomeric Transition Observed in a Conductive One-Dimensional Rhodium-Dioxolene Complex.

The exploration of dynamic molecular crystals is a fascinating theme for materials scientists owing to their fundamental science and potential application to molecular devices. Herein, a one-dimensional (1D) rhodium-dioxolene complex is reported that exhibits drastic changes in properties with the phase transition. X-ray photoelectron spectroscopy (XPS) revealed that the room-temperature (RT) phase is in a mixed-valence state, and therefore, the drastic changes originate from the mixed-valence state appearing in the RT phase.

Proton Order-Disorder Phenomena in a Hydrogen-Bonded Rhodium-η(5)-Semiquinone Complex: A Possible Dielectric Response Mechanism.

A newly synthesized one-dimensional (1D) hydrogen-bonded (H-bonded) rhodium(II)-η(5)-semiquinone complex, [Cp*Rh(η(5)-p-HSQ-Me4)]PF6 ([1]PF6; Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; HSQ = semiquinone) exhibits a paraelectric-antiferroelectric second-order phase transition at 237.1 K. Neutron and X-ray crystal structure analyses reveal that the H-bonded proton is disordered over two sites in the room-temperature (RT) phase.

Multifunctional one-dimensional rhodium(I)-semiquinonato complex: substituent effects on crystal structures and solid-state properties.

Two new one-dimensional (1D) rhodium(I)-semiquinonato complexes formulated as [Rh(3,6-DBSQ-4,5-PDO)(CO)2]∞ (4; 3,6-DBSQ-4,5-PDO(•-) = 3,6-di-tert-butyl-4,5-(1,3-propanedioxy)-1,2-benzosemiquinonato) and [Rh(3,6-DBSQ-4,5-(N,N'-DEN))(CO)2]∞ (5; 3,6-DBSQ-4,5-(N,N'-DEN)(•-) = 3,6-di-tert-butyl-4,5-(N,N'-diethylenediamine)-1,2-benzosemiquinonato) were synthesized to explore the nature of the unusual structural phase transition and magnetic and conductive properties recently reported for [Rh(3,6-DBSQ-4,5-(MeO)2)(CO)2]∞ (3; 3,6-DBSQ-4,5-(MeO)2(•-) = 3,6-di-tert-butyl-4,5-dimethoxy-1,2-benzosemiquinonato). Their crystal structures and magnetic and conductive properties were investigated. Compounds 4 and 5 comprise neutral 1D chains of complex molecules stacked in a staggered arrangement with fairly short average Rh-Rh distances of 3.

Bistable multifunctionality and switchable strong ferromagnetic-to-antiferromagnetic coupling in a one-dimensional rhodium(I)-semiquinonato complex.

We present a comprehensive study of the synthesis, heat capacity, crystal structures, UV-vis-NIR and mid-IR spectra, DFT calculations, and magnetic and electrical properties of a one-dimensional (1D) rhodium(I)-semiquinonato complex, [Rh(3,6-DBSQ-4,5-(MeO)2)(CO)2]∞ (3), where 3,6-DBSQ-4,5-(MeO)2(•-) represents 3,6-di-tert-butyl-4,5-dimethoxy-1,2-benzosemiquinonato radical anion. The compound 3 comprises neutral 1D chains of complex molecules stacked in a staggered arrangement with short Rh-Rh distances of 3.0796(4) and 3.

A one-dimensional platinum mixed-valence complex with bridging thiocyanate S atoms: [[Pt(II)(en)2](μ-SCN)[Pt(IV)(en)2](μ-SCN)](ClO4)4 (en is ethane-1,2-diamine).

A new one-dimensional platinum mixed-valence complex with nonhalogen bridging ligands, namely catena-poly[[[bis(ethane-1,2-diamine-κ(2)N,N')platinum(II)]-μ-thiocyanato-κ(2)S:S-[bis(ethane-1,2-diamine-κ(2)N,N')platinum(IV)]-μ-thiocyanato-κ(2)S:S] tetrakis(perchlorate)], {[Pt(2)(SCN)(2)(C(2)H(8)N(2))(4)](ClO(4))(4)}(n), has been isolated. The Pt(II) and Pt(IV) atoms are located on centres of inversion and are stacked alternately, linked by the S atoms of the thiocyanate ligands, forming an infinite one-dimensional chain. The Pt(IV)-S and Pt(II)···S distances are 2.

Multiple-decker phthalocyaninato dinuclear lanthanoid(III) single-molecule magnets with dual-magnetic relaxation processes.

The SMM behaviour of dinuclear Ln(III)-Pc multiple-decker complexes (Ln = Tb(3+) and Dy(3+)) with energy barriers and slow-relaxation behaviour were explained by using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of several dinuclear Ln(III)-Pc type SMMs have never been discussed on the basis of the crystal structure. For dinuclear Tb(III)-Pc complexes, a dual magnetic relaxation process was observed.

On the nature of the multiple ground states of the MMX mixed-valence chain compound, [Pt(II/III)2(n-PenCS2)4I]∞.

We present a comprehensive study of the temperature dependence of the crystal structure using single-crystal X-ray diffraction and diffuse scattering, and electrical transport and magnetic properties as well as some optical properties at room temperature to elucidate the origin and the form of multiple ground states demonstrated in a previous study of the heat-capacity of the MMX chain compound, [Pt(II/III)(2)(n-PenCS(2))(4)I](∞). The present results confirm the presence of the two phase transitions, one reversible of first order at 207 K and the other nonreversible monotropic at 324 K, separating the low temperature (LT), room temperature (RT), and high temperature (HT) phases. The unit cell displays a 3-fold periodicity of -Pt-Pt-I- in the RT and HT phases because of the structural disorder which is exhibited by the dithiocarboxylato groups and the n-pentyl groups belonging to the central diplatinum unit.

Polymorphic crystal approach to changing the emission of [AuCl(PPh3)2], analyzed by direct observation of the photoexcited structures by X-ray photocrystallography.

The photoexcited charge-transferred state of [AuCl(PPh(3))(2)] in a novel polymorphic crystal form was directly observed by X-ray photocrystallographic analysis. Its photoexcited state was completely different from the one generated in the known crystal of [AuCl(PPh(3))(2)]; the photoexcited bond-shrunk state was generated in the known crystal. This difference in the generated photoexcited state was clearly reflected by the difference in emission color.

Flexibility of cubane-like Cu4I4 framework: temperature dependence of molecular structure and luminescence thermochromism of [Cu4I4(PPh3)4] in two polymorphic crystalline states.

Multitemperature X-ray structure analyses and photoemission spectra of [Cu(4)I(4)(PPh(3))(4)] in two polymorphic crystals reveal that the cubane-like framework is flexibly distorted effecting luminescence thermochromism.

Syntheses, structures and solid-state properties of MMX mixed-valence chains, [Ni(II/III)2(RCS2)4I]infinity (R = Et, n-Pr and n-Bu): evidence of a spin-Peierls transition.

The partial oxidation of [Ni(II/II)(2)(RCS(2))(4)] (R = Et (1), n-Pr (2), and n-Bu (3)) with iodine affords the MMX chain compounds [Ni(II/III)(2)(RCS(2))(4)I](infinity) (R = Et (4), n-Pr (5), and n-Bu (6)), respectively. The crystal structures of 4-6 consist of neutral one-dimensional (1-D) chains with a repeating -Ni-Ni-I- unit. The room-temperature (RT) structure of 4 indicates a charge-polarization (CP) state {-Ni((2.

X-ray diffractometry for the structure determination of a submicrometre single powder grain.

A high-precision diffractometer has been developed for the structure analysis of a submicrometre-scale single grain of a powder sample at the SPring-8 BL40XU undulator beamline. The key design concept is the combination of a stable focused synchrotron radiation beam and the precise axis control of the diffractometer, which allows accurate diffraction intensity data of a submicrometre-scale single powder grain to be measured. The phase zone plate was designed to create a high-flux focused synchrotron radiation beam.

Synthesis of orthorhombic Mo-V-Sb oxide species by assembly of pentagonal Mo6O21 polyoxometalate building blocks.

Mix and match: The pentagonal [Mo(6)O(21)](n-) polyoxomolybdate building block assembles with other sources of Mo, V, and Sb ions to form an orthorhombic Mo-V-Sb oxide. The first single-crystal X-ray analysis of an orthorhombic Mo-V-based oxide, a promising catalyst for light alkane selective oxidation known as the "M1 phase", revealed the structure of the compound.

Structure and electronic configuration of an iron(II) complex in a LIESST state: a pump and probe method.

Two polymorphs of mononuclear six-coordinate iron(II) spin-crossover complex trans-[Fe(tzpy)(2)(NCS)(2)] (tzpy = 3-(2-pyridyl)[1,2,3]triazolo[1,5-a]pyridine) (1) were isolated and structurally characterized. According to the thermally dependent magnetic measurements, polymorph A undergoes a gradual spin transition from a paramagnetic high-spin state ((5)T(2), S = 2, HS-1) above 200 K to a diamagnetic low-spin state ((1)A(1), S = 0, LS-1) below 120 K, whereas polymorph B shows an abrupt spin transition with T(1/2) at 102 K. Molecular and crystal structures of polymorph A in the HS-1 and LS-1 states were studied at 300 and 40 K, respectively.

Photochromism of an organorhodium dithionite complex in the crystalline-state: molecular motion of pentamethylcyclopentadienyl ligands coupled to atom rearrangement in a dithionite ligand.

In the crystalline state, the rhodium dinuclear complex [(RhCp*)(2)(mu-CH(2))(2)(mu-O(2)SSO(2))] (1) with a photoresponsive dithionite group (mu-O(2)SSO(2)) and two pentamethylcyclopentadienyl ligands (Cp* = eta(5)-C(5)Me(5)) undergoes a 100% reversible unimolecular type T inverse photochromism upon interconversion to [(RhCp*)(2)(mu-CH(2))(2)(mu-O(2)SOSO)] (2). The photochromism can be followed directly by using stepwise crystal structure analysis (Angew. Chem.

Constructing highly conducting metal-metal bonded solids by electrocrystallization of [Pt(II)2(RCS2)4] (RCS2(-) = dithiocarboxylato, R = methyl or ethyl).

Partially oxidized one-dimensional (1D) Pt-Pt chain compounds [Pt2(MeCS2)4]4ClO4.5PhCN (1) and [Pt2(EtCS2)4]5(ClO4)2 (2) were synthesized by electrocrystallization of diplatinum(II,II) complexes from different solvents. 1 and 2 consist of 1D Pt-Pt chains of stacked Pt-Pt dimers with short interdimer S.

Ultra-high-precision time control system over any long time delay for laser pump and synchrotron x-ray probe experiment.

An ultra-high-precision clock system for long time delay has been developed for picosecond time-resolved x-ray diffraction measurements using synchrotron radiation (SR) pulses and synchronized femtosecond laser pulses. The time delay control between pump laser pulse and the probe SR pulse was achieved by combining an in-phase quadrature modulator and a synchronous counter. This method allowed us to change the delay time by a nearly infinite amount while maintaining the precision of +/-8.

Anthracene array-type porous coordination polymer with host-guest charge transfer interactions in excited states.

Confinement of electron donor guests affords an efficient, photo-induced charge transfer (CT) with the anthracene moieties of a porous coordination polymer.

Syntheses and unusual segregated-alternated hybrid stacking structure of hydrogen-bonded charge-transfer complexes composed of bis[2,3-pyridinedithiolate]metal complexes.

We report the syntheses of new planar electron donor inorganic molecules [bis(2,3-pyridinedithiolate)metal(II)]; [MII(Hpydt)2] (M = Ni(1), Pd(2), Pt(3)) and their anions; [MII(pydt)2]2- (M = Ni(4), Pd(5)), which are equipped with both a highly lying highest occupied molecular orbital (HOMO) perpendicular to the plane and hydrogen-bonding capability in the plane. In addition, we present two novel hydrogen-bonded charge-transfer (HBCT) complexes, [M(Hpydt)2]TCNQ (M = Ni, Pd), with 7,7,8,8-tetracyanoquinodimethane (TCNQ). All the neutral and ionic inorganic molecules and the HBCT complexes were successfully characterized by single-crystal X-ray crystallography.

Alkyl group as entropy reservoir in an MMX chain complex, Pt2(n-PenCS2)4I.

Heat capacity of halogen-bridged one-dimensional binuclear metal complex (so-called MMX chain) having four n-pentyl groups, Pt2(n-PenCS2)4I, was measured by adiabatic calorimetry. A first-order phase transition was observed at 207.4 K when measurement was made after cooling from room temperature.