Elucidation of Electronic Structures of Mixed-Valence States Induced by dσ-π Charge Delocalization in Linear-Chain and Discrete Rhodium-Dioxolene Tetrameric Complexes.

We have successfully synthesized unique linear-chain and discrete mixed-valence tetrameric complexes, {[Rh(3,6-DBDiox-4,5-SCO)(CO)]·hexane} () and [Rh(3,6-DBDiox-4,5-SCO)(CO)] (), by carefully choosing the solvent. X-ray photoelectron spectra (XPS) confirm that and are in the Rh(I,II) mixed-valence state. Analyses of the metrical oxidation state (MOS) of dioxolene ligands reveal that in and , the electron density corresponding to one electron per tetramer is transferred from Rh(I) ions to semiquinonato ligands, and the transferred charge is delocalized throughout the four dioxolene ligands.

Redox-triggered reversible modulation of intense near-infrared and visible absorption using a paddlewheel-type diruthenium(III) complex.

A new paddlewheel-type diruthenium complex with 2-amino-3-(trifluoromethyl)pyridine (amtfmp) [Ru2(amtfmp)4Cl2] ([1]), which shows intense and characteristic near-infrared (NIR) and visible absorption, has been developed and structurally characterized by single crystal X-ray diffraction (SCXRD) analyses. This complex exhibits reversible and dramatic NIR and visible electrochromic behavior from deep-blue ([1]) to pink ([1]-) due to the ON-OFF switching of its characteristic ligand-to-metal charge transfer (LMCT) and d-d absorption bands in response to an external voltage or chemical reagent such as decamethylcobaltocene (CoCp*2). The one-electron reduced species of [1], i.

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.

Detailed magnetic analysis and successful deep-neural-network-based conformational prediction for [VO(dmso)][BPh].

Pentakis(dimethylsulfoxide-κ)oxidovanadium(iv) bis(tetraphenylborate), [VO(dmso)][BPh] (dmso: dimethylsulfoxide), was synthesized, and its pseudo- VO coordination geometry was revealed by a single-crystal X-ray method. A novel equation set was obtained for magnetic susceptibility and magnetization of the d complexes, considering the axial distortion and the spin-orbit coupling for the D free-ion term. The equation set enabled magnetic simulation for significantly symmetry-lowered d complexes to obtain the anisotropic -values and also the excitation energies.

Paddlewheel-type diruthenium(iii,iii) tetrakis(2-aminopyridinate) complexes with NIR absorption features: combined experimental and theoretical study.

The reactions of [Ru(OCCH)Cl] with 2-aminopyridine (Hamp) and 2-amino-4-methylpyridine (Hammp) afforded two novel Ru complexes, [Ru(amp)Cl] (1) and [Ru(ammp)Cl] (2), respectively. Single crystal X-ray diffraction analyses revealed that 1 and 2 adopted typical paddlewheel-type structures, where the Ru units are coordinated with four aminopyridinate ligands with a cis-2:2 arrangement at the equatorial positions and two chloride ligands at the axial positions. The stabilities of 1 and 2 were supported by unrestricted density functional theory (uDFT) calculations.

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.

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.

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.

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.

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.