Abstract
Four chiral Schiff base binuclear 3d-4f complexes (NdNi, NdCu, GdNi, and GdCu) have been prepared and characterized by means of electronic and CD spectra, IR spectra, magnetic measurements, and X-ray crystallography (NdNi). A so-called artifact peak of solid state CD spectra, which was characteristic of oriented molecules without free molecular rotation, appeared at about 470 nm. Magnetic data of the complexes in the solid state (powder) and in PMMA cast films or solutions indicated that only GdCu preserved molecular structures in various matrixes of soft maters. For the first time, we have used the changes of intensity of artifact CD peaks to detect properties of environmental (media solid state (KBr pellets), PMMA cast films, concentration dependence of PMMA in acetone solutions, and pure acetone solution) for chiral 3d-4f complexes (GdCu). Rigid matrix keeping anisotropic orientation exhibited a decrease in the intensity of the artifact CD peak toward negative values. The present results suggest that solid state artifact CD peaks can be affected by environmental viscosity of a soft mater matrix.
Highlights
Organic/inorganic hybrid materials containing photochromic organic dyes and transition metal complexes such as models of chiral catalysts [1,2,3] and magnetic materials [4,5,6,7,8] have been developedInt
-called artifact peaks may sometimes be a serious problem for solid state Circular dichroism (CD) spectra [16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31], in which chiral molecules take anisotropic orientation without a degree of freedom for molecular motion
Among four chiral 3d-4f complexes reported only GdCu was confirmed to be suitable for CD spectroscopy experiments in various environmental matrixes
Summary
Organic/inorganic hybrid materials containing photochromic organic dyes and transition metal complexes such as models of chiral catalysts [1,2,3] and magnetic materials [4,5,6,7,8] have been developed. -called artifact peaks may sometimes be a serious problem for solid state CD spectra [16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31], in which chiral molecules take anisotropic orientation without a degree of freedom for molecular motion This problem has mainly been dealt with in view of improvement to reduce noise of CD spectra in the solid state, investigation in soft mater matrixes (intermediate between isotropic solutions and anisotropic solids) or positive applications for obtaining useful information have not been carried out so far. As far as we know, we attempt to use the intensity of artifact CD peaks exhibiting environmental dependence of soft mater matrixes for the first time
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