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[en] The real sample temperatures during the nuclear resonant vibrational spectroscopy on biological samples have been assessed and significantly reduced (116 → 52 K) by improving the sample-loading procedures. There are several practical and intertangled issues which make the experiments of nuclear resonant vibrational spectroscopy (NRVS) on biological samples difficult to perform. The sample temperature is one of the most important issues. In NRVS the real sample temperatures can be very different from the readings on the temperature sensors. In this study the following have been performed: (i) citing and analyzing various existing NRVS data to assess the real sample temperatures during the NRVS measurements and to understand their trends with the samples’ loading conditions; (ii) designing several NRVS measurements with (Et_4N)[FeCl_4] to verify these trends; and (iii) proposing a new sample-loading procedure to achieve significantly lower real sample temperatures and to balance among the intertangled experimental issues in biological NRVS measurements

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[en] Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF₃, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe₂(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]}₂O, and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C_4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe^IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe^III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.

[en] Second harmonic generation (SHG) from a short-period structure composed of alternating antiferromagnetic (AF) and ionic-crystal layers is investigated, where the generated harmonic waves are situated in the far-infrared range and attributed to the magnetically nonlinear interaction in AF layers. The presence of a kind of appropriate ionic-crystal layers in the structure can support negative refraction for the pumping wave and positive refraction for the SH wave, so the SHG is greatly amplified in the vicinity of each AF resonant frequency. For the composite structure FeF₂/TlBr, we found that the SH output is about 8 times higher than that of the FeF₂ bulk in the same frequency range. - Highlights: ► Second harmonic generation of an antiferromagnetic/ionic-crystal composite is studied. ► The multilayered composite medium possesses negative refraction for the pumping wave. ► Second harmonic output of the composite is 8 times that of antiferromagnetic bulk.

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