Molecular magnets

Among all C-, N-, and O-centered polyradicals, high-spin nitrenes possess the largest magnetic anisotropy and are of considerable interest as multi-level molecular spin systems for exploration of organic molecular magnetism and quantum information processing. Although the first representatives of quintet and septet nitrenes were obtained almost 50 years ago, the experimental and theoretical studies of these highly reactive species became possible only recently, owing to new achievements in molecular spectroscopy and computational chemistry. Meanwhile, dozens of various quintet dinitrenes and septet trinitrenes were successfully characterized by IR, UV/Vis, and EPR spectroscopy, thus providing important information about the electronic structure, magnetic properties and reactivity of these compounds

Persistent organic high-spin trinitrenes

The septet ground state trinitrenes 1,3,5‐trichloro‐2,4,6‐trinitrenobenzene and 1,3,5‐tribromo‐2,4,6‐trinitrenobenzene were isolated in inert (Ar, Ne, and Xe) as well as reactive matrices (H$_2$, O$_2$, and H$_2$O) at cryogenic temperatures. These trinitrenes were obtained in high yields by UV photolysis of the corresponding triazides and characterized by IR and UV/Vis spectroscopy. The trinitrenes, despite bearing six unpaired electrons, are remarkably unreactive towards molecular oxygen and hydrogen and are persistent in water ice up to 160 K where the water matrix starts to sublime off

The mystery of the benzene-oxide/oxepin equilibrium

The equilibrium between benzene oxide (1) and oxepin (2) is of large importance for understanding the degradation of benzene in biological systems and in the troposphere. Our studies reveal that at cryogenic temperatures, this equilibration is governed by rare heavy-atom tunneling. In solid argon at 3 K, 1 rearranges to 2 via tunneling with a rate constant of approximately 5.3×10−5 s−1. Thus, in a nonpolar environment, 2 is slightly more stable than 1, in agreement with calculations at the CCSD(T) level of theory. However, if the argon is doped with 1 % of H2O or CF3I as typical hydrogen or halogen bond donors, respectively, weak complexes of 1 and 2 are formed, and now 2 is tunneling back to form 1. Thus, by forming non-covalent complexes, 1 becomes slightly more stable than 2 and the direction of the heavy-atom tunneling is reversed

Chirality control of a single carbene molecule by tip-induced van der Waals interactions

Non-covalent interactions such as van der Waals interactions and hydrogen bonds are crucial for the chiral induction and control of molecules, but it remains difficult to study them at the single-molecule level. Here, we report a carbene molecule on a copper surface as a prototype of an anchored molecule with a facile chirality change. We examine the influence of the attractive van der Waals interactions on the chirality change by regulating the tip-molecule distance, resulting in an excess of a carbene enantiomer. Our model study provides insight into the change of molecular chirality controlled by van der Waals interactions, which is fundamental for understanding the mechanisms of chiral induction and amplification

Heavy-atom tunneling in semibullvalenes

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene $\bf {2 a}$ and 3,7-dicyano-1,5-dimethylsemibullvalene $\bf {2 b}$ were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in $\bf {2 a}$ and $\bf {2 b}$, two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of $\bf {2 b}$ in cryogenic matrices were found to be smaller than the ones of $\bf {2 a}$ under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of $\bf {2 b}$ compared to that of $\bf {2 a}$ results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for $\bf {2 a}$ in a qualitatively different way than for $\bf {2 b}$