Strain-Controlled Spin Transition in Heterostructured Metal-Organic Framework Thin Film.

Metal-organic framework (MOF) thin films have recently attracted much attention as a new platform for surface/interface research, where unconventional structural and physical properties emerge. Among the many MOFs as candidates for fabrication of thin films, Hofmann-type MOFs {Fe(pz)[M(CN)]} [pz = pyrazine; M = Ni (), M = Pt ()] are attractive, because they undergo spin transitions with concomitant structural changes. Here, we demonstrate the first example of a strain-controlled spin transition in heterostructured MOF thin films.

Chiral crystallization of a zinc(II) complex.

The compound, {6,6'-dimeth-oxy-2,2'-[(4-azaheptane-1,7-di-yl)bis-(nitrilo-meth-an-yl-idyne)]diphenolato}zinc(II) methanol monosolvate, [Zn(CHNO)]·CHOH, at 298 K crystallizes in the ortho-rhom-bic space group P2. The Zn atom is coordinated by a penta-dentate Schiff base ligand in a distorted trigonal-bipyramidal NO geometry. The equatorial plane is formed by the two phenolic O and one amine N atom.

Crystallographic and Computational Electron Density of d Orbitals of Azo-Schiff Base Metal Complexes Using Conventional Programs.

The crystal structures of two azobenzene derivative Schiff base metal complexes (new CHCuNO of -1 and known CHMnNO of 2/c abbreviated as Cu and Mn, respectively) were (re-)determined experimentally using conventional X-ray analysis to obtain electron density using a PLATON program. Cu affords a four-coordinated square planar geometry, while Mn affords a hexa-coordinated distorted octahedral geometry whose apical sites are occupied by an acetate ion and water ligands, which are associated with hydrogen bonds. The π-π or CH-π and hydrogen bonding intermolecular interactions were found in both crystals, which were also analyzed using a Hirshfeld surface analysis program.

Success or Failure of Chiral Crystallization of Similar Heterocyclic Compounds.

Single crystals of two achiral and planar heterocyclic compounds, CHHO() and CHNO (), recrystallized from ethanol, were characterized by single crystal X-ray analysis, respectively, and chiral crystallization was observed only for as 222 (# 19), whereas it was not observed for 2/c (# 14). In , as a monohydrate, the hydrogen bonds were pronounced around the water of crystallization (O4), and the planar cyclic sites were arranged in parallel to slightly tilted positions. On the other hand, an anhydride formed a dimer by hydrogen bonds between adjacent molecules in the crystal, which were aggregated by van der Waals forces and placed in parallel planar cyclic sites.

Crystal structure and Hirshfeld surface analysis of (aqua-κ)(methanol-κ)[-(2-oxido-benzyl-idene)threoninato-κ ,,']copper(II).

In the title complex mol-ecule, [Cu(CHNO)(CHO)(HO)], the Cu atom is coordinated in a distorted square-pyramidal geometry by a tridentate ligand synthesized from l-threonine and salicyl-aldehyde, one methanol mol-ecule and one water mol-ecule. In the crystal, the mol-ecules show intra- and inter-molecular O-H⋯O hydrogen bonds. The Hirshfeld surface analysis indicates that the most important contributions to the packing are H⋯H (49.

Degradation of Human Serum Albumin by Infrared Free Electron Laser Enhanced by Inclusion of a Salen-Type Schiff Base Zn (II) Complex.

A salen-type Schiff base Zn(II) complex included in human serum albumin (HSA) protein was examined by UV-Vis, circular dichroism (CD), and fluorescence (PL) spectra. The formation of the composite material was also estimated by a GOLD program of ligand-protein docking simulation. A composite cast film of HSA and Zn(II) complex was prepared, and the effects of the docking of the metal complex on the degradation of protein molecules by mid-infrared free electron laser (IR-FEL) were investigated.

Investigation by DFT Methods of the Damage of Human Serum Albumin Including Amino Acid Derivative Schiff Base Zn(II) Complexes by IR-FEL Irradiation.

An infrared free electron laser (IR-FEL) can decompose aggregated proteins by excitation of vibrational bands. In this study, we prepared hybrid materials of protein (human serum albumin; HSA) including several new Schiff base Zn(II) complexes incorporating amino acid (alanine and valine) or dipeptide (gly-gly) derivative moieties, which were synthesized and characterized with UV-vis, circular dichroism (CD), and IR spectra. Density functional theory (DFT) and time dependent DFT (TD-DFT) calculations were also performed to investigate vibrational modes of the Zn(II) complexes.

Co-crystallization of 3,5-di-nitro-benzoic acid with two anti-psychotic agents: a simple 1:1 salt with trihexyphenidyl and a 1:2 acid salt containing a very short O-H⋯O hydrogen bond with chlorprothixene.

Co-crystallization of racemic 1-cyclo-hexyl-1-phenyl-3-(piperidin-1-yl)propan-1-ol (trihexyphenid-yl) with 3,5-di-nitro-benzoic acid gives a simple 1:1 salt, namely 1-(3-cyclo-hexyl-3-hy-droxy-3-phenyl-prop-yl)piperidin-1-ium 3,5-di-nitro-benzoate, CHNO·CHNO , (I), whereas a similar co-crystallization using ()-3-(2-chloro-9-thioxanthen-9-yl)-,-di-methyl-propan-1-amine (chlorprothixene) gives a 1:2 acid salt, namely ()-3-(2-chloro-9-thioxanthen-9-yl)-,-di-methyl-propan-1-aminium hydrogen bis-(3,5-di-nitro-benzoate), CHClNS·[H(CHNO)], (II), the anion of which contains a very short O-H⋯O hydrogen bond, with dimensions O-H = 1.04 (3) Å, H⋯O = 1.41 (3) Å, O⋯O = 2.

Three closely related 1-[(1,3-benzodioxol-5-yl)methyl]-4-(halobenzo-yl)piperazines: similar mol-ecular structures but different inter-molecular inter-actions.

In each of the compounds 1-[(1,3-benzodioxol-5-yl)methyl]-4-(3-fluoro-benzo-yl)piperazine, CHFNO (I), 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,6-di-fluoro-benzo-yl)piperazine, CHFNO (II), and 1-[(1,3-benzodioxol-5-yl)methyl]-4-(2,4-di-chloro-benzo-yl)piperazine, CHClNO (III), the piperazine rings adopt a chair conformation with the (1,3-benzodioxol-5-yl)methyl substituent occupying an equatorial site: the five-membered rings are all slightly folded across the O⋯O line leading to envelope conformations. The dihedral angle between the planar amidic fragment and the haloaryl ring is 62.97 (5)° in (I) but 77.

Crystal structure of 3,6-dihy-droxy-4,5-di-methyl-benzene-1,2-dicarbaldehyde.

The title compound, CHO, was synthesized from tetra-methyl-1,4-benzo-quinone. In the crystal, the almost planar mol-ecule (r.m.

Crystal structure of ()-3-[(2,6-di-methyl-phen-yl)diazen-yl]-7-methyl-1-indazole.

The title azo compound, CHN, was synthesized from 2,6-di-methyl-aniline. The diazenyl group adopts a () conformation, with an N=N bond length of 1.265 (4) Å.

A highly crystalline oriented metal-organic framework thin film with an inorganic pillar.

We report a step-by-step route to fabricate the first example of a crystalline oriented metal-organic framework thin film having an anionic inorganic pillar ligand, {Cu(4,4'-bipyridyl)(SiF)}. X-ray study and sorption analysis revealed its high crystallinity and porous character.

Fabrication and Structural Characterization of an Ultrathin Film of a Two-Dimensional-Layered Metal-Organic Framework, {Fe(py)[Ni(CN)]} (py = pyridine).

We report the fabrication and characterization of the first example of a tetracyanonickelate-based two-dimensional-layered metal-organic framework, {Fe(py)Ni(CN)} (py = pyridine), thin film. To fabricate a nanometer-sized thin film, we utilized the layer-by-layer method, whereby a substrate was alternately soaked in solutions of the structural components. Surface X-ray studies revealed that the fabricated film was crystalline with well-controlled growth directions both parallel and perpendicular to the substrate.

Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film.

Fabrication of thin films made of metal-organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs.

A three-dimensional accordion-like metal-organic framework: synthesis and unconventional oriented growth on a surface.

We describe the synthesis and sorption properties of a new metal-organic framework (MOF), Fe(H2O)2(bpy)[Pt(CN)4]·H2O (bpy = 4,4'-bipyridine), with a three-dimensional accordion-like structure. Although crystalline oriented MOF thin films reported to date have been mainly limited to a layer-type structure, we succeeded in the fabrication of its crystalline oriented thin film.

Remarkable Lattice Shrinkage in Highly Oriented Crystalline Three-Dimensional Metal-Organic Framework Thin Films.

Highly oriented crystalline thin films of metal-organic frameworks (MOFs) have promising practical applications, such as in gas separation, catalysis, and sensing. We report on the successful fabrication of highly oriented crystalline thin films of three-dimensional porous MOFs, Fe(pz)[M(CN)4] (M = Ni, Pd; pz = pyrazine). Synchrotron X-ray diffraction studies reveal not only the highly oriented crystalline nature but also the remarkable shrunken structure of the thin films (∼3-7% volume shrinkage) compared with bulk samples.

Step-by-step fabrication of a highly oriented crystalline three-dimensional pillared-layer-type metal-organic framework thin film confirmed by synchrotron X-ray diffraction.

Fabrication of a crystalline ordered thin film based on the porous metal-organic frameworks (MOFs) is one of the practical applications of the future functional nanomaterials. Here, we report the creation of a highly oriented three-dimensional (3-D) porous pillared-layer-type MOF thin film on a metal substrate using a step-by-step approach based on liquid-phase epitaxy. Synchrotron X-ray diffraction (XRD) study clearly indicates that the thin film is crystalline and its orientation is highly controlled in both horizontal and vertical directions relative to the substrate.