Guest Modulation of Spin‐Crossover Transition Temperature in a Porous Iron(II) Metal–Organic Framework: Experimental and Periodic DFT Studies

The synthesis, structure, and magnetic properties of three clathrate derivatives of the spin‐crossover porous coordination polymer {Fe(pyrazine)[Pt(CN)₄]} ( 1 ) with five‐membered aromatic molecules furan, pyrrole, and thiophene is reported. The three derivatives have a cooperative spin‐crossover transition with hysteresis loops 14–29 K wide and average critical temperatures T_c=201 K ( 1?fur ), 167 K ( 1?pyr ), and 114.6 K ( 1?thio ) well below that of the parent compound 1 (T_c=295 K), confirming stabilization of the HS state. The transition is complete and takes place in two steps for 1?fur , while 1?pyr and 1?thio show 50 % spin transition. For 1?fur the transformation between the HS and IS (middle of the plateau) phases occurs concomitantly with a crystallographic phase transition between the tetragonal space groups P4/mmm and I4/mmm, respectively. The latter space group is retained in the subsequent transformation involving the IS and the LS phases. 1?pyr and 1?thio display the tetragonal P4/mmm and orthorhombic Fmmm space groups, respectively, in both HS and IM phases. Periodic calculations using density functional methods for 1?fur , 1?pyr , 1?thio , and previously reported derivatives 1?CS₂ , 1?I, 1?bz (benzene), and 1?pz (pyrazine) have been carried out to investigate the electronic structure and nature of the host–guest interactions as well as their relationship with the changes in the LS–HS transition temperatures of 1?Guest . Geometry‐optimized lattice parameters and bond distances in the empty host 1 and 1?Guest clathrates are in general agreement with the X‐ray diffraction data. The concordance between the theoretical results and the experimental data also comprises the guest molecule orientation inside the host and intermolecular distances. Furthermore, a general correlation between experimental T_c and calculated LS–HS electronic energy gap was observed. Finally, specific host–guest interactions were studied through interaction energy calculations and crystal orbital displacement (COD) curve analysis.     

Studies on an antibody-coated tube method of aldosterone

We studied on the basic performance of a non-extraction coated tube RIA kit, DPC Aldosterone kit (Nippon DPC Corporation). 1. The average binding CVs of the calibrators (25 to 1,200 pg/ml) were stable in a range from 1.4 to 1.9%. 2. The minimum sensitivity was 17 pg/ml from 2SD method of 0 calibrator. 3. The intra-assay reproducibility test showed an average CV as 9.0%, and the inter-assay test showed as 8.8%. 4. The recovery ratios of a recovery test were 85.4 to 121.6%. 5. The correlation test with another maker's kit showed a correlation curve as y = 0.970 x + 19.68 and a correlation coefficiency as r = 0.970. 6. The normal range, the correlation between fasting recumbency and daytime sitting, and the correlation between walking and resting, showed similar results as former reports.     

Talbot interferometry with an adaptive light intensity compensator

Talbot interferometry with a larger applicable scope has been investigated based on the intensity amplification method to weak moiré fringes by using photorefractive crystal as a light amplifier. It not only has function of conventional Talbot interferometry, but also is suitable for situations such as weak incident beam and detected object with strong absorption. The investigation indicates that the method or technique is feasible and the results of theoretical analysis are verified by experiments. Based on this investigation, Talbot interferometry with an adaptive light intensity compensator is proposed and some merits and demerits of the technique have briefly been discussed.     

Carbon-13 nuclear magnetic resonance spectra of some methyl and phenyl substituted 2H-azirines

Carbon-13 n.m.r. spectra have been obtained for some methyl and phenyl substituted 2H-azirines. The higher field resonance of C-2 than that of the corresponding aziridine carbon is interpreted in terms of ring strain. Substituent effects on the chemical shifts of the azirine ring carbons are discussed. A set of additivity parameters for the methyl and phenyl groups are obtained which can be used for the calculation of the chemical shifts of the azirine ring carbons. The substituent effect of an azirine ring on the chemical shift of benzene is also discussed in comparison with those of some other substituents. A high degree of s character (48.5%) in the exocyclic orbital of C-3 is indicated by a large J(¹³C-3,H) value (242.5 Hz).     

Raman scattering from mixed crystals (HgBr2)1−x(HgI2)x

The behavior of long wavelength optic phonons in mixed system HgBr₂-HgI₂ has been investigated in Raman scattering. Different types of behavior, i.e. ‘persistent type’ and ‘amalgamation type’ were observed. Three strong Raman bands were observed for persistent type mode. These correspond to stretching vibration of HgBr₂, HgBrI, HgI₂ molecules. Intensity of these bands showed striking concentration dependence. A model based on nearly free molecular approximation have been proposed to explain the dependence. The analysis indicated that the distribution of anions on the sublattices is essentially random. For amalgamation (one-mode) type behavior, it is suggested that the intramolecular force relevant to the vibration is comparable to the intermolecular force and that the band width of the corresponding phonon branch in the parent crystal is broad enough to be degenerate with impurity mode at the low concentration limit.     

Entanglement of angular momenta of atoms and molecules

In this article, we investigate the entanglement degrees of angular momenta of atoms and molecules. We demonstrate theoretically and numerically the guidelines, how to prepare maximally entangled states and how the entanglement of the angular momenta changes by changing the quantum numbers of atoms and molecules. We show that the entanglement degree reduces to the Clebsch–Gordan coefficients frequently encountered in angular momentum theory. The maximally entangled states found in this manner are useful for quantum computers and quantum information science. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Phase separation in dilute LiCl-H2O solution related to the polyamorphism of liquid water

When an emulsified 4.8 mol % LiCl-H2O solution was cooled under a pressure of 0.35 or 0.45 GPa and decompressed to 0.1 GPa at 142 K, slightly above its glass transition temperature (approximately 140 K at 0.1 GPa), its volume increased suddenly. This was regarded as an appearance of the low-density amorphous ice in the liquid solution as suggested by x-ray and Raman measurements, and this appearance corresponded to the high-to-low-density polyamorphic transition of pure H2O. Hysteresis was considered to accompany this volumetric change. The hysteresis of the liquid transition proves its first-order nature and, as for the solution, this suggests that the transition is a polyamorphic phase separation.     

The chemistry of localized singlet 1,3-diradicals (biradicals): from putative intermediates to persistent species and unusual molecules with a π-single bonded character

Localized singlet diradicals (biradicals) are key intermediates in chemical reactions involving homolytic bond-cleavage and formation processes. The molecular structure and electronic structure had been historically elusive due to the short-lived character of the reactive intermediates. In the last 15 years, a significant development of singlet diradical chemistry was achieved after the pioneering findings of long-lived singlet diradicals. In this tutorial review, the recent development of localized singlet diradical chemistry is summarized and discussed. The following subjects are included (a) the mechanism by which the ground state spin-multiplicity of localized 1,3-diradicals is controlled; (b) the substituent and heteroatom effect on the most stable electronic configuration of the singlet 1,3-diradicals, type-1 versus type-2; (c) the molecular design for the long-lived singlet ground state diradicals; (d) the generation and characterization of the singlet diradicals; and (e) the future prospects.     

Synchronized stereocontrol of planar chirality by crystallization-induced asymmetric transformation

Synchronized stereocontrol of two planar-chiral units was accomplished by using crystallization-induced asymmetric transformation (CIAT) of cyclophane-type bridged bisnicotinate derivatives 5b and 7. After screening various linkers, (S)-2-amino-1-butanol and (S)-tert-leucinol were found to be the most effective for CIAT of the corresponding bridged bisnicotinate 5b and 7, respectively, whose diastereomeric ratio finally reached 97% and 88%, respectively.     

Gas‐phase basicities of acetophenones toward lanthanum cation [La(OMe)]

The relative free energy changes (lanthanum cation basicity, LaCB[L₂]) for the reaction [La(OMe)₂]L ? La(OMe) + 2L were determined in the gas phase for m‐ and p‐substituted acetophenones based on the measurement of ligand exchange equilibria using an FT‐ICR mass spectrometer. The substituent effect on ΔLaCB[L₂] of acetophenone is described in terms of the Yukawa–Tsuno equation, ΔG = ρ(σ° + r⁺ Δ σ ), with a ρ value of ?11.2 and an r⁺ value of 0.49. From this result, a ρ value of ?7.0 and an r⁺ value of 0.49 were estimated for the monomeric complex [LLa(OMe)] with the aid of theoretical calculations. This ρ value was found to be significantly smaller than that for protonation, and even smaller than Li⁺ basicity. Such a small ρ value has been attributed to the largely ionic (ion–dipole interaction) nature of the bonding interaction between La(OMe) and the carbonyl oxygen atom and, in part, to the long distance between La(OMe) and the substituent. Contrary to the ρ value, the r⁺ value is identical in both La(OMe) and Li⁺ basicities, suggesting that the r⁺ value of 0.49 can be regarded as a limiting one in a series of Lewis cation basicities of the acetophenone system, H⁺ (0.86) > Me₃Si⁺ (0.75) > Me₃Ge⁺ (0.71) > Cu⁺ (0.60) > Li⁺ = La(OMe) (0.49). Since the binding interaction between La(OMe) or Li⁺ and a neutral ligand is mostly electrostatic, the moderate r⁺ was interpreted to result from the redistribution of the induced positive charge within the acetophenone moiety upon binding with a metal ion rather than transfer of positive charge from a metal ion to the aromatic moiety. Copyright © 2010 John Wiley & Sons, Ltd.