Intramolecular London Dispersion Interactions Do Not Cancel in Solution.

We present a comprehensive experimental study of a di-t-butyl-substituted cyclooctatetraene-based molecular balance to measure the effect of 16 different solvents on the equilibrium of folded versus unfolded isomers. In the folded 1,6-isomer, the two t-butyl groups are in close proximity (H···H distance ≈ 2.5 Å), but they are far apart in the unfolded 1,4-isomer (H···H distance ≈ 7 Å). We determined the relative strengths of these noncovalent intramolecular σ-σ interactions via temperature-dependent nuclear magnetic resonance measurements. The origins of the interactions were elucidated with energy decomposition analysis at the density functional and ab initio levels of theory, pinpointing the predominance of London dispersion interactions enthalpically favoring the folded state in any solvent measured.

Identification and Reactivity of s-cis,s-cis-Dihydroxycarbene, a New [CH2O2] Intermediate.

We report the first preparation of the s-cis,s-cis conformer of dihydroxycarbene (1cc) by means of pyrolysis of oxalic acid, isolation of the lower-energy s-trans,s-trans (1tt) and s-cis,s-trans (1ct) product conformers at cryogenic temperatures in a N2 matrix, and subsequent narrow-band near-infrared (NIR) laser excitation to give 1cc. Carbene 1cc converts quickly to 1ct via quantum-mechanical tunneling with an effective half-life of 22 min at 3 K. The potential energy surface features around 1 were pinpointed by convergent focal point analysis targeting the AE-CCSDT(Q)/CBS level of electronic structure theory. Computations of the tunneling kinetics confirm the time scale of the 1cc → 1ct rotamerization and suggest that direct 1cc → H2 + CO2 decomposition may also be a minor pathway. The intriguing latter possibility cannot be confirmed spectroscopically, but hints of it may be present in the measured kinetic profiles.

Control of Excited-State Conformations in B,N-Acenes.

We present a new concept to control the conformations of molecules in the excited state through harvesting negative hyperconjugation. The strategy was realized with the 2,3,1,4-benzodiazadiborinane scaffold, which was prepared by a new synthetic procedure. Photochemical studies identified dual light emission, which was assigned to well-defined conformers. The emission at longer wavelength can be switched off by restricting the rotational degrees of freedom in the solid state as well as by controlling the energy levels of the excited states through adjusting the solvent polarity.

TUNNEX: An easy-to-use wentzel-kramers-brillouin (WKB) implementation to compute tunneling half-lives.

Tunneling in experiments (TUNNEX) is a free open-source program with an easy-to-use graphical user interface to simplify the process of Wentzel-Kramers-Brillouin (WKB) computations. TUNNEX aims at experimental chemists with basic knowledge of computational chemistry, and it offers the computation of tunneling half-lives, visualization of data, and exporting of graphs. It also provides a helper tool for executing the zero-point vibrational energy correction along the path. The program also enables computing high-level single points along the intrinsic reaction path. TUNNEX is available at https://github.com/prs-group/TUNNEX. As the WKB approximation usually overestimates tunneling half-lives, it can be used to screen tunneling processes before proceeding with elaborate kinetic experiments or higher-level tunneling computations such as instanton theory and small curvature tunneling approaches. © 2018 Wiley Periodicals, Inc.

Stable Organic Neutral Diradical via Reversible Coordination.

We report the formation of a stable neutral diboron diradical simply by coordination of an aromatic dinitrogen compound to an ortho-phenyldiborane. This process is reversible upon addition of pyridine. The diradical species is stable above 200 °C. Computations are consistent with an open-shell triplet diradical with a very small open-shell singlet-triplet energy gap that is indicative of the electronic disjointness of the two radical sites. This opens a new way of generating stable radicals with fascinating electronic properties useful for a large variety of applications.

London Dispersion Enables the Shortest Intermolecular Hydrocarbon H···H Contact.

Neutron diffraction of tri(3,5-tert-butylphenyl)methane at 20 K reveals an intermolecular C-H···H-C distance of only 1.566(5) Å, which is the shortest reported to date. The compound crystallizes as a C3-symmetric dimer in an unusual head-to-head fashion. Quantum chemical computations of the solid state at the HSE-3c level of theory reproduce the structure and the close contact well (1.555 Å at 0 K) and emphasize the significance of packing effects; the gas-phase dimer structure at the same level shows a 1.634 Å C-H···H-C distance. Intermolecular London dispersion interactions between contacting tert-butyl substituents surrounding the central contact deliver the decisive energetic contributions to enable this remarkable bonding situation.

Conformer-specific hydrogen atom tunnelling in trifluoromethylhydroxycarbene.

Conformational control of organic reactions is at the heart of the biomolecular sciences. To achieve a particular reactivity, one of many conformers may be selected, for instance, by a (bio)catalyst, as the geometrically most suited and appropriately reactive species. The equilibration of energetically close-lying conformers is typically assumed to be facile and less energetically taxing than the reaction under consideration itself: this is termed the 'Curtin-Hammett principle'. Here, we show that the trans conformer of trifluoromethylhydroxycarbene preferentially rearranges through a facile quantum-mechanical hydrogen tunnelling pathway, while its cis conformer is entirely unreactive. Hence, this presents the first example of a conformer-specific hydrogen tunnelling reaction. The Curtin-Hammett principle is not applicable, due to the high barrier between the two conformers.

Polytwistane.

Twistane, C10H16, is a classic D2-symmetric chiral hydrocarbon that has been studied for decades due to its fascinating stereochemical and thermodynamic properties. Here we propose and analyze in detail the contiguous linear extension of twistane with ethano (ethane-1,2-diyl) bridges to create a new chiral, C2-symmetric hydrocarbon nanotube called polytwistane. Polytwistane, (CH)n, has the same molecular formula as polyacetylene but is composed purely of C(sp(3))-H units, all of which are chemically equivalent. The polytwistane nanotube has the smallest inner diameter (2.6 Å) of hydrocarbons considered to date. A rigorous topological analysis of idealized polytwistane and a C236H242 prototype optimized by B3LYP density functional theory reveals that the polymer has a nonrepeating, alternating σ-helix, with an irrational periodicity parameter and an instantaneous rise (or lead) angle near 15 °. A theoretical analysis utilizing homodesmotic equations and explicit computations as high as CCSD(T)/cc-pVQZ yields the enthalpies of formation Delta(f)H(0)°(twistane) = -1.7 kcal mol(-1) and Delta(f)H(0)°(polytwistane) = +1.28 kcal (mol CH)(-1), demonstrating that the hypothetical formation of polytwistane from acetylene is highly exothermic. Hence, polytwistane is synthetically viable both on thermodynamic grounds and also because no obvious pathways exist for its rearrangement to lower-lying isomers. The present analysis should facilitate the preparation and characterization of this new chiral hydrocarbon nanotube.