Pure α-metallated benzyllithium from a single-crystal-to-single-crystal transition.

International audienc

Intramolecular charge transfer with 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) and other aminobenzonitriles. A comparison of experimental vapor phase spectra and crystal structures with calculations.

Calculations of molecular structures in the electronic ground state So and of excited state and fluorescence energies generally refer to the gas phase. This complicates a comparison with experimental data, which often are only available for molecules in solution. Therefore, experimental absorption and fluorescence spectra in the vapor phase are presented for 1-fert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6), 1-methy1-6-cyano-1,2,3,4-tetrahydroquinoline (NMC6), 4-(dimethylamino)benzonitrile (DMABN), and 4-(diisopropylamino)benzonitrile (DIABN). NTC6 and DIABN show a dual fluorescence in the gas phase, with emissions from an intramolecular charge transfer (ICT) and a locally excited (LE) state, whereas with NMC6 and DMABN only LE emission is observed. For a comparison of the experimental molecular structure in So with the results of recent computations, X-ray crystal structures of NTC6, NMC6, and several analogues are presented. For DMABN, NMC6, and NTC6, LE/ICT energy diagrams are constructed, in which the experimental energies of the Franck-Condon singlet excited states Si and S2, and the LE and ICT states together with their emissions, are compared with the calculations. The LE and ICT dipole moments are also discussed. This comparison reveals substantial differences, in particular for the ICT energies, but even for the structure of the So ground states. It is concluded that the computed ICT states of NTC6 and DMABN, in which the full conjugation of the phenyl ring is interrupted, is different from the ICT states measured in the experiments

Trapping x‐ray radiation damage from homolytic Se–C bond cleavage in BnSeSeBn crystals (Bn=benzyl, CH2C6H5)

Irradiation of dibenzyl diselenide BnSeSeBn with X-ray or UV-light cleaves the Se-C and the Se-Se bonds, inducing stable and metastable radical states. They are inevitably important to all natural and life sciences. Structural changes due to X-ray-induced Se-C bond-cleavage could be pin-pointed in various high-resolution X-ray diffraction experiments for the first time. Extended DFT methods were applied to characterize the solid-state structure and support the refinement of the observed residuals as contributions from the BnSeSe • radical species. The X-ray or UV-irradiated crystalline samples of BnSeSeBn were characterized by solid-state EPR. This paper provides insight that in the course of X-ray structure analysis of selenium compounds not only organo-selenide radicals like RSe • may occur, but also organo diselenide BnSeSe • radicals and organic radicals R • are generated, particularly important to know in structural biology

Synthesis and Crystal Structure of a Copper(II) Benzoate Complex Bearing a Bis-2,2′-Tetrahydrofuryl Peroxide Moiety

Complex [Cu2(ben)4·2THF−(η1–O2)]∞ (2) (ben=C6H5CO2− benzoate; THF=tetrahydrofuran) was isolated when a solution of Cu2(ben)4·2THF (1) in THF upon natural sunlight irradiation yields crystals suitable for single-crystal X-ray diffraction analysis. 2, crystallized in the C2/c monoclinic space group, Z=8, V=3394.2 (4) Å3, and the unit cell parameters a=9.7935(7) Å, b=19.0055 (13) Å, c=18.2997 (13) Å, α=90°, β=94.7996 (11)º and γ=90°. This is the first example of a polymeric copper(II) carboxylate compound stabilizing a peroxo group via its apical ligand (THF molecule). Additionally, 2 was also characterized by elemental analysis, Fourier-transformed infrared spectroscopy (FTIR) and Raman spectroscopyUniversidad de Costa Rica/[804-B7-279]/UCR/Costa RicaUniversidad de Costa Rica/[804-B0-650]/UCR/Costa RicaUCR::Vicerrectoría de Docencia::Ciencias Básicas::Facultad de Ciencias::Escuela de QuímicaUCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro de Investigación en Electroquímica y Energía Química (CELEQ