The interest of circular dichroism in the solid state is stimulated by several needs, such as the desire to get solvent free spectra, the insolubility of the sample or the intrinsic process in which the sample itself is prepared or manipulated. We approach the argument on the basis of the sampling technique, since each different case calls for specific care in getting proper results.

Solid-state diffuse reflectance circular dichroism (DRCD) spectra of some chiral lambda- and delta-M[(A--A)(n)](m+) coordination compounds [M(III) = Cr, Co; A--A = ethylendiamine (en), O,O'-2(R)3(R)dimethylethylene dithiophosphate ion, (R,R)bdtp(-), sepulchrate (Sep); n = 1, 3; m = 0, 3] were measured and compared with their solution, nujol mull, and KBr pellet spectra in the spectral region of 300-800 nm. The validity of the DRCD method to obtain reliable CD spectra which reflect a correct absolute configuration at the metal coordination center as well as subtle changes in the stereochemistry of the compound in the solid vs. solution states was proved. DRCD is the only spectroscopic method to examine randomly oriented chiral compounds without the effect of pressure, solvent, or diluting media such as KBr or nujol (which lends the sample irrecoverable and may interact with the sample), and directly relate to the structure that is revealed by X-ray diffractometry.

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Alkylation of the alpha-carbanion of (R)-(-)-tert-butyl methyl sulfoxide (4) with n-propyl bromide afforded (+)-n-butyl tert-butyl sulfoxide (1) to which the absolute configuration (R) was ascribed. This assignment was confirmed by X-ray analysis of the complex 6 obtained from the enantiomerically pure sulfoxide (-)-1 and mercury chloride. Vibrational absorption and circular dichroism spectra of (+)-1 were measured in CDCl3 solution in the 2000-900 cm(-1) region and compared with the ab initio predictions of absorption and VCD spectra obtained with density functional theory using the B3LYP/6-31G basis set for different conformers of (R)-1. This comparison indicated also that (+)-1 is of the (R)-configuration.

A new class of chiral oligothiophenes is described. Mono-, bi-, ter-, and quarterthiophenes have been linked to enantiopure trans-1,2-cyclohexanediamine (DACH) via diamino or diimino moieties. The stereochemistry of DACH, the type of linker, and oligothiophene size determine the conformational flexibility of these molecules and consequently their molecular and supramolecular helicity in solution and in the solid state. The case of diaminobis(bithiophene), which inverts helicity and shows chiral amplification in the transition from solution to film, is described in detail. Based on the combined use of circular dichroism in solution and in the solid state, single-crystal/thin-film X-ray diffraction, and polarized optical microscopy, a working mechanism has been proposed to explain this unexpected behavior.

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Chiral Discrimination of Complexes with Dj, Symmetry. Synthesis and Characterization of Tris{0,0'-bis[(+)(S)-2-methylbutyl] dithiophosphato}chromium(III) Complexes (AA){Cr[(+)(S)(S)Mebdtp]3} and A-(-)589-and A-(+)589{Cr[(+)(S)(S)Mebdtp]3} and Crystal Packing of Racemic Tris{0,0 -diethyl dithiophosphato}chromium(III), Cr[ddtp]3