Synthesis and Properties of Partially Saturated Fluorenyl-Derived [n]Helicenes Featuring an Overcrowded Alkene

The straightforward, multigram-scale synthesis of the partially saturated H₆-fluoreno[n]helicenes (n=5 or 7) featuring a central, overcrowded alkene is described. The key cyclization step was based on an intramolecular McMurry reaction from the corresponding 1,5-diketones. Chiral stationary phase HPLC analysis and isomer separation indicate that each helicenic compound is constituted of three diastereoisomers at room temperature, i. e. the configurationally stable (R,R,P)/(S,S,M) pair of enantiomers and an apparently achiral compound resulting from the rapid interconversion between the (R,S,P) and (S,R,M) enantiomers. The partially saturated H₆-fluoreno[n]helicenes are oxidatively aromatized to give an efficient access to the corresponding fluoreno[n]helicenes. The chiroptical properties (vibrational and electronic circular dichroism) of the chiral, enantiopure compounds have been measured and analyzed by quantum-chemical calculations, confirming their helicoidal nature.     

Phosphahelicenes: From Chiroptical and Photophysical Properties to OLED Applications

Herein, the experimental physicochemical and chiroptical properties of a series of phosphahelicenes are reported, focusing on their UV/Vis absorption, luminescence, electronic circular dichroism, optical rotations, and circularly polarized luminescence. Furthermore, detailed analysis of absorption and ECD spectra performed with the help of quantum-chemical calculations allowed us to highlight general features of these helicenic phosphines. Finally, due to well-suited electrochemical properties and thermal stability, the systems were successfully used as emitters in organic light-emitting diodes.     

Synthesis and vibrational circular dichroism of enantiopure chiral oxorhenium(V) complexes containing the hydrotris(1-pyrazolyl)borate ligand

The infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl)borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation (symmetry breaking due to the weak nuclear force). New chiral oxorhenium complexes have been synthesized, namely, [TpReO(eta2-O(CH3)CH2CH2O-O,O)] (4a and 4b) diastereomers and [TpReO(eta2-N(CH3)CH2CH2O-N,O)] (5) and [TpReO(eta2-N(tBu)CH2CH2O-N,O)] (6) enantiomers. All compounds could be obtained in enantiomerically pure form by using either column chromatography or HPLC over chiral columns. VCD spectroscopy of these compounds and of [TpReO(eta2-N(CH3)CH(CH3)CH(Ph)O-N,O)] (2) and [TpReO(eta2-N(CH2)3CHCO2-N,O)] (3) (with chiral bidentate ligands derived, respectively, from ephedrine and proline) were studied. This allowed the absolute configuration determination of all compounds together with their conformational analysis, by comparing calculated and experimental spectra. This is the first VCD study of rhenium complexes which further demonstrates the applicability of VCD spectroscopy in determining the chirality of inorganic complexes.     

Optical Activity of Spin-Forbidden Electronic Transitions in Metal Complexes from Time-Dependent Density Functional Theory with Spin-Orbit Coupling

The calculation of magnetic transition dipole moments and rotatory strengths was implemented at the zeroth-order regular approximation (ZORA) two-component relativistic time-dependent density functional theory (TDDFT) level. The circular dichroism of the spin-forbidden ligand-field transitions of tris(ethylenediamine)cobalt(III) computed in this way agrees very well with available measurements. Phosphorescence dissymmetry factors and the corresponding lifetimes are evaluated for three N-heterocyclic-carbene-based iridium complexes, two of which contain helicene moieties, and for two platinahelicenes. The agreement with experimental data is satisfactory. The calculations reproduce the signs and order of magnitude of , and the large variations of phosphorescence lifetimes among the systems. The electron spin contribution to the magnetic transition dipole moment is shown to be important in all of the computations.     

Absolute configuration of C76 from optical rotatory dispersion.

The absolute configuration of C76 has been determined as (+)589-(fC)-C76 , for the first time, by comparing the experimental and predicted optical rotatory dispersion (ORD) patterns. The experimental ORD pattern was derived from the experimental electronic circular dichroism (ECD) spectrum using the Kramers-Kronig (KK) transform. The theoretical ORD spectra were calculated in the resonant region using linear response theory, and also using the KK transform of the theoretical ECD spectrum, at different theoretical levels, namely BHLYP/6-31G*, B3LYP/6-31G*, BLYP/6-31G*, and HF/6-31G*. Good agreement noted between experimental and predicted spectra allows for an unambiguous determination of the absolute configuration.     

SOME FURTHER CONSIDERATIONS ON THE USE OF REPAIR-DEFECTIVE ORGANISMS AS BIOLOGICAL DOSIMETERS FOR BROAD-BAND ULTRAVIOLET RADIATION SOURCES

Abstract— The extreme variation in biological effectiveness of the various components of solar ultraviolet radiation (solar UV) which reaches the earth's surface, especially photons of wavelengths between 295 and 330 nm, makes the dosimetry of solar UV a complex and, as yet, unresolved problem. A proper weighting of the various components of solar UV would permit expression of expsoure as a single parameter (dose). Weighting could compensate for the variations in composition of solar UV which might occur during exposure or the differences in sources of UV radiations; weighting would permit comparison of exposures at various locations on the earth and extrapolation of laboratory observations to field situations where wavelength composition might be rather different. Various radiation-sensitive microorganisms have been proposed as biological dosimeters. Biological dosimeters automatically weight the subcomponents of solar UV differently than a purely physical irradiance meter. We have examined the available evidence regarding the weighting which repair-defective mutants provide in comparison with response of a number of wild-type organisms and would caution investigators that, for broad-band UV sources, especially those with significant biological actions through the range of 300–330 nm, repair-sensitive mutants may improperly weight the components, leading to errors of dosimetry and thus to possible errors of interpretation of results of solar UV exposure of wild-type organisms     

Counterion dependent dye aggregates: nanorods and nanorings of tetra(p-carboxyphenyl)porphyrin

Atomic force microscopy (AFM) of porphyrin aggregates formed on silica from acidic aqueous solution is used to investigate the basis for the previously reported counterion dependence of the optical spectra of aggregates of H(2)TCPP(2+), the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP). Resonance light scattering confirms the presence of excitonically coupled porphyrin aggregates in solutions of H(2)TCPP(2+) in both aqueous HCl and HNO(3). Aggregates formed in aqueous HNO(3) solutions show resonance light scattering (RLS) at wavelengths within both the H and J aggregate absorption bands and are imaged on the surface of silica as nanorods about 3 to 4 nm in height. H(2)TCPP(2+) aggregates in aqueous HCl solution exhibit RLS when excited within the blue-shifted Soret band (H band) and produce AFM images on silica of ring-shaped structures ranging from about 200 to 2000 nm in diameter. Fluorescence excitation and emission spectra reveal quenching of the Q-band emission in the aggregates at a pH less than 1 and confirm the existence of a single species, assigned to a dimer, at a pH just above 1. The morphology of the nanostructures as revealed by AFM provides insight into the structural basis for the counterion-dependent optical properties of H(2)TCPP(2+) aggregates.