Synthesizing Chiral Hydrocarbazoles with a Tetrasubstituted Carbon Using Holmium-Catalyzed Enantioselective [4 + 2] Cycloaddition: Mechanistic Insights from Luminescence and DFT Studies.

This study analyzes the feasibility of utilizing the catalytic and enantioselective [4 + 2] cycloaddition of sterically demanding heterocycle-incorporated siloxydienes to yield polycyclic skeletons with a tetrasubstituted carbon. A catalyst derived from lanthanide triflimide enabled the reaction. The mechanistic investigations and transformations of the adducts are also discussed. The proposed approach facilitates the synthesis of intricate polysubstituted skeletons, each with multiple contiguous chiral centers, thereby aiding in the production of diverse hydrocarbazoles for drug discovery purposes.

Thermosensitive visible-light-excited visible-/NIR-luminescent complexes with lanthanide sensitized by the π-electronic system through intramolecular H-bonding.

Visible-luminescent lanthanide (LnL) complexes with a highly planar tetradentate ligand were successfully developed for a visible-light solid-state excitation system. L was designed by using two 2-hydroxy-3-(2-pyridinyl)-benzaldehyde molecules bridged by ethylenediamine, which was then coordinated to a series of Ln ions (Ln = Nd, Sm, Eu, Gd, Tb, Dy, and Yb). From the measurement of single-crystal X-ray analysis of EuL, two phenolic O atoms and two imine N atoms in L were coordinated to the Eu ion, and each π-electronic system took coplanar with the edged-pyridine moiety through an intramolecular hydrogen bond. The enol group on the phenolic skeleton changed to the keto form, and the pyridine was protonated. Thus, intramolecular proton transfer occurred in L after the complexation. Other complexes take isostructure. The space group is P-1, and the c-axis shrinks with decreasing temperature without a phase transition in EuL. The yellow color caused by the planar structure of L can sensitize ff emission by visible light, and the luminescence color of each complex depends on central Ln ions. Furthermore, a phosphorescence band also appeared at rt with ff emission in LnL. Drastic temperature dependence of luminescence was clarified quantitatively.

Asymmetric Lumino-Transformer: Circularly Polarized Luminescence of Chiral Eu(III) Coordination Polymer with Phase-Transition Behavior.

A chiral Eu(III) coordination polymer with phase-transition behavior, [Eu(+tfc)3(m-dpeb)]n, (+tfc: (+)-3-trifluoroacetylcamphorato, m-dpeb: 1,3-bis(diphenylphosphorylethynyl)benzene) was reported for understanding the effect of polymer chain arrangement (orientation effect) on the circularly polarized luminescence (CPL) in a solid system. The phase-transition behavior of the transformable Eu(III) coordination polymer was characterized using differential scanning calorimetry and powder X-ray diffraction. The Eu(III) coordination polymer exhibited phase transition at approximately 180 °C. The magnitude of the CPL intensity was drastically changed because of the phase transition, without coordination geometrical change around the Eu(III) ion. In this study, the orientation effect of a chiral Eu(III) coordination polymer on the CPL properties in crystalline solid is demonstrated.

Magnetism in a helicate complexes arising with the tetradentate ligand.

The synthesis of [M(dimphen)(NCS)2] (1; M = FeII), (2; M = CoII), (3; M = MnII) and [Fe(dimphen)(NCSe)2] (4), where dimphen = [1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane], are reported. The crystal packing structures of 1-3, show intermolecular π-π stacking and NCSSCN interactions. The complex 1 shows ferromagnetic interaction, and the complex 2 displays single-molecular magnet behaviour.

Electrofluorochromic Device Based on a Redox-Active Europium(III) Complex.

Electrofluorochromism owing to redox reactions on the center europium (Eu) ion in ionic liquids is examined for the helicate complexes (abbreviated as EuL) with a hexadentate pyridine derivative. Typical electrofluorochromism requires extra electroactive units complementing intra- or intermolecular energy transfer to quench fluorophores. Herein, an unprecedentedly simplified electrofluorochromic system overcoming such issues is demonstrated by utilizing reversible electrochemistry of EuL between Eu3+ and Eu2+, which accompanies large emission transition. A three-electrode electrochemical switching device is facilely prepared with an ionic liquid [BMIM][PF6] and EuL mixture. Benefiting from the stable helical coordinated structure of the ligand in [BMIM][PF6], highly enhanced red fluorescence of EuL with small quantity (≤1 wt %) is utilized. Rapid response and large contrast of luminescence are achieved: the emission is drastically quenched at the reduced state (Eu2+) and it is successfully restored by subsequent oxidation (Eu3+). The reversible fluctuation of excitation and emission spectra of an electrofluorochromic device is achieved in the potential window within ±2 V. The device affords excellent optoelectric properties in terms of well-controlled luminescence switching depending on the applied potentials and its durability. This work paves an efficient and smart way toward Eu luminescence control in optoelectronic devices.

Solvent-Dependent Bending Ability of Salen-Derived Organic Crystals.

The formation of plastic or brittle organic crystals of salen derivatives that depend on the solvents employed for crystallization is demonstrated. Large yellow crystals (ranging from mm to cm size) of ten different salen derivatives were obtained and investigated. Among them, (bis(2-hydroxyacetophenone)ethylenediimine) 2, which was recrystallized from dichloromethane, tetrahydrofuran or chloroform, exhibited plastic deformation behaviour when mechanical force was applied to the (001) face. In contrast, when 2 was recrystallized from benzene, brittle crystals were obtained. Face indexing confirmed that different crystal faces were obtained by depending on the solvent employed for recrystallization, which leads to either flexible (plastic) or brittle crystals. Photoluminescence with a band maximum at 510 nm and thermochromism related to tautomerism between OH and NH forms were also investigated, and indicate that 2 is a flexible organic single-crystal material with multifunctional properties.

Chiroptical Spectroscopic Studies on Lanthanide Complexes with Valinamide Derivatives in Solution.

Ligands based on 2,2'-bipyridine and valinamide moieties induce circularly polarized luminescence in their europium complexes. Both the R and S enantiomers of the complexes were successfully obtained. Single-crystal X-ray analysis of the racemic crystal confirmed that the ligand is coordinated to the europium ion in a tetradentate fashion. The π-electronic system of the ligand is co-planar with the valinamide moiety, and acts as an efficient photoantenna to sensitize europium luminescence by UV excitation. The luminescence quantum yield (QY) of europium in the valinamide-containing complex was 44 % in acetonitrile. The glum value to evaluate the circularly polarized luminescence was relatively high at |0.13| estimated from their magnetic dipole transitions around 593 nm. For comparison, we prepared hexadentate europium complexes in the S- and R-forms derived from two bipyridine moieties linked by ethylenediamines. The determined QYs were 18 % (S) and 16 % (R), and the glum value |0.12| for the hexadentate complexes. The photophysical properties of the gadolinium complexes of the ligands were also evaluated.

Water-dependent charge-transfer-induced spin transition of Prussian blue analogues.

Cobalt-iron Prussian blue analogues are magnetic functional compounds that exhibit charge-transfer-induced spin transition (CTIST), however, the role of guest species such as water in influencing the magnetic behaviour has remained unclear. Here, we report the water-dependent CTIST behaviour of Na0.46Co[Fe(CN)6]0.78(H2O)1.31 together with its single crystal X-ray structural analysis, for the first time.

Metal Dilution Effects on the Reverse Spin Transition in Mixed Crystals of Type [Co(1-x)Zn(x)(C16-terpy)2](BF4)2 (x = 0.1-0.7).

Metal dilution effects on reverse spin transition (rST) in mixed crystals of type [Co(1-x)Zn(x)(C16-terpy)2](BF4)2 (x = 0.1-0.7) were investigated by comparison with behavior of [Co(1-x)Fe(x)(C16-terpy)2](BF4)2 (x = 0.1-0.4). In the mixed crystals, the Zn complexes increased rST temperatures linearly with increasing values of x, without changing the hysteresis width, while the Fe complexes decreased rST temperatures. Moreover, the strength of the metal dilution effects in the CoZn mixed crystals is weaker than what occurs in the CoFe mixed crystals.

Synthesis of mesoporous materials as nano-carriers for an antimalarial drug.

An antimalarial drug artesunate (ATS) was encapsulated in both functionalized MCM-41 and ordinary MCM-41 with an excellent loading capacity and sustained release behavior for possible biomedical applications.

Molecular Designs for Enhancement of Polarity in Ferroelectric Soft Materials.

The racemic oxovanadium(IV) salmmen complexes, [VO((rac)-(4-X-salmmen))] (X = C12C10C5 (1), C16 (2), and C18 (3); salmmen = N,N'-monomethylenebis-salicylideneimine) with "banana shaped" molecular structures were synthesized, and their ferroelectric properties were investigated. These complexes exhibit well-defined hysteresis loops in their viscous phases, moreover, 1 also displays liquid crystal behaviour. We observed a synergetic effect influenced by three structural aspects; the methyl substituents on the ethylene backbone, the banana shaped structure and the square pyramidal metal cores all play an important role in generating the observed ferroelectricity, pointing the way to a useful strategy for the creation of advanced ferroelectric soft materials.

Crystal structure of bis-[4'-(1,4,7,10-tetra-oxa-13- aza-cyclo-penta-decan-13-yl)-2,2':6',2''-terpyridine]-cobalt(III) tris-(perchlorate) methanol monosolvate monohydrate.

In the title compound, [Co(C25H30N4O4)2](ClO4)3·CH3OH·H2O, the metal atom is coordinated by two tridentate crown ether terpyridine ligands, forming a distorted CoN6 octa-hedron. The three pyridine rings in each crown-terpyridine ligand are approximately coplanar [maximum deviations = 0.088 (12) and 0.102 (15) Å] and the mean planes through the three pyridine rings are perpendicular to each other, making a dihedral angle of 89.95 (17)°. An intra-molecular C-H⋯π inter-action is observed between the two terpyridine ligands. In the crystal, O-H⋯O and C-H⋯O hydrogen bonds, a π-π stacking inter-action [centroid-centroid distance = 3.923 (7) Å] and a C-H⋯π inter-action connect the complex cation, the perchlorate anions and the two types of solvent molecules, forming a three-dimensional network.

Spin-crossover behaviors in solvated cobalt(ii) compounds.

Two solvated cobalt(ii) terpyridine complexes, [Co(MeO-terpy)2](BF4)2·H2O (·H2O) and [Co(MeO-terpy)2](BF4)2·acetone (·acetone) were prepared. Annealing each of these complexes resulted in the formation of two desolvated species, and , respectively. ·H2O and exhibited two-step and gradual SCO. The compound ·acetone has high-spin at all temperatures and undergoes a reverse spin transition due to a phase change.