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This TOC represents the Polarity dependent charge separation of BODIPY dimer (3D). The charge transfer lifetime (1 ps for MeOH and 0.5 ps for DMF) has been confirmed using femtosecond transient absorption spectroscopy. 

Bicyclo[3.2.1]oct-2-yne was generated from the Fritsch–Buttenberg–Wiechell rearrangement of 2-norbornylidene carbene. The rearrangement preferentially involves migration of a tertiary carbon over a secondary carbon, a trend that contrasts with rearrangements of acyclic carbenes and which may be attributable to hyperconjugative effects promoted by the bridged structure of the carbene. 

The realization of multifunctional nanoparticle systems is essential to achieve highly efficient catalytic materials for specific applications; however, their production remains quite challenging. They are typically achieved through the incorporation of multiple inorganic components; however, incorporation of functionality could also be achieved at the organic ligand layer. In this work, we demonstrate the generation of multifunctional nanoparticle catalysts using peptide-based ligands for tandem catalytic functionality. To this end, chimeric peptides were designed that incorporated a Au binding sequence and a catalytic sequence which can drive ester hydrolysis. Using this chimera, Au nanoparticles were prepared, which sufficiently presented the catalytic domain of the peptide to drive tandem catalytic processes occurring at the peptide ligand layer and the Au nanoparticle surface. This work represents unique pathways to achieve multifunctionality from nanoparticle systems tuned by both the inorganic and bio/organic components, which could be highly important for applications beyond catalysis, including theranostics, sensing, and energy technologies. 

Abstract Nitrenium ions are important reactive intermediates in both chemistry and biology. Although singlet nitrenium ions are well-characterized by direct methods, the triplet states of nitrenium ions have never been directly detected. Here, we find that the excited state of the photoprecursor partitions between heterolysis to generate the singlet nitrenium ion and intersystem crossing (ISC) followed by a spontaneous heterolysis process to generate the tripletp-iodophenylnitrenium ion (np). The triplet nitrenium ion undergoes ISC to generate the ground singlet state, which ultimately undergoes proton and electron transfer to generate a long-lived radical cation that further generates the reduced p-iodoaniline. Ab Initio calculations were performed to map out the potential energy surfaces to better understand the excited state reactivity channels show that an energetically-accessible singlet-triplet crossing lies along theN-Nstretch coordinate and that the excited triplet state is unbound and spontaneously eliminates ammonia to generate the triplet nitrenium ion. These results give a clearer picture of the photophysical properties and reactivity of two different spin states of a phenylnitrenium ion and provide the first direct glimpse of a triplet nitrenium ion.