Buchbesprechungen

Ohne Zusammenfassung     

Buchbesprechungen

Ohne Zusammenfassung     

Synthesis,Vibrational Spectrum and Structure of the Tetracyanoborate K[B(CN)4]·CH3CN

The new tetracyanoborate K[B(CN)₄]·CH₃CN was synthesized by dissolution of the solvent‐free K[B(CN)₄] in acetonitrile and subsequent careful crystallization. The crystal structure has been determined by single‐crystal X‐ray diffraction. It crystallizes in the orthorhombic space group P2₁2₁2₁ with Z = 4. Some comparisons with related structures are made, and the vibrational spectrum is discussed.     

Host-guest interactions in the supramolecular incorporation of fullerenes into tailored holes on porphyrin-modified gold nanoparticles in molecular photovoltaics

Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. The porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C60 composites (second step). Large composite clusters with a size of 200-400 nm were grown from the supramolecular complex of porphyrin-C60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C60 ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2 electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle. Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photovoltaics.     

An NMR study of the rotational barriers in cobalt-stabilized carbocations: X-ray crystal structures of (η-C4Ph4)Co-(η-C5H4R), where R is CH3CO, CHO, CH(Bu)OH

Treatment of the aldehyde (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-CHO) (4b) with tert-butyllithium or phenyllithium yields the secondary alcohols (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-CH(R)OH), where R=tert-butyl (5) or phenyl (6). Protonation of 5 and 6 at −80 °C furnishes the deep purple, cobalt-stabilized cations, 7 and 8, respectively, both of which exhibit restricted rotation about the external C₅H₄-CHR⁺ linkage on the NMR time-scale. These data indicate a minimum value for the barrier to rotation of 15 kcal mol⁻¹, but it is certainly much higher, indicating a considerable degree of C-C double bond character. X-ray crystal structures of 4b, 5 and also of the ketone (η⁴-C₄Ph₄)Co(η⁵-C₅H₄-C(O)CH₃ (4a) are reported. The secondary alcohol 5 exhibits disorder in the solid state because of the presence of diastereomers as a consequence of the stereogenic center at the α-carbon and the clockwise or anticlockwise propeller orientations of the tetraphenylcyclobutadiene ligand.