Borylenes, RB, are elusive reactive intermediates. Still not much is known about their excited states from spectroscopic experiments, and existing knowledge is limited to diatomic borylenes only. The electronic structure and geometry of borylenes with diverse substituents on boron (where R = H, F, Cl, CH3, CF3, tBu, NH2, Ph, and SiMe3) were studied by means of computational chemistry. For this purpose, geometries of borylenes in their lowest singlet and triplet states were optimized at the B3LYP/def2-TZVP level of theory. Additionally, the influence of substitution on the energies of frontier molecular orbitals, HOMO-LUMO energy gaps, singlet-triplet energy splittings, and excitation energies was investigated. Two lowest vertical singlet-singlet excitations were computed using EOM-CCSD and TD-DFT (using hybrid B3LYP, and long-range separated CAM-B3LYP and ωB97X functionals) in combination with the aug-cc-pVTZ basis set. The electronic transitions involve excitations from nonbonding sp boron orbital (HOMO) mainly to empty p(B) orbitals and partially to the orbitals of the substituent, and are of n → π* type. The results can facilitate prospective identification of borylenes, e.g., in UV-vis matrix isolation or time-resolved spectroscopy experiments.

CdSe nanocrystals and aggregates of an aryleneethynylene derivative are assembled into a hybrid thin film with dual fluorescence from both fluorophores. Under continuous excitation, the nanocrystals and the molecules exhibit anti-correlated fluorescence intensity variations, which become periodic at low temperature. We attribute this to a structure-dependent aggregation induced emission of the aryleneethynylene derivative, which impacts the rate of excitation energy transfer between the molecules and nanocrystals. Energy transfer also affects the electric transport properties of the hybrid material under optical excitation. This work highlights that combining semiconductor nanocrystals with molecular aggregates, which exhibit aggregation induced emission, can result in unprecedented emerging optical properties.

Nitroxyl (HNO) and hydrogen peroxide have both been implicated in a variety of reactions relevant to environmental and physiological processes and may contribute to a unique, unexplored, pathway for the production of nitrous acid (HONO) in soil. To investigate the potential for this reaction, we report an in-depth investigation of the reaction pathway of HO and HNO forming HONO and water. We find the breaking of the peroxide bond and a coupled proton transfer in the first step leads to hydrogen nitryl (HNO) and an endogenous water, with an extrapolated NEVPT2 (multireference perturbation theory) barrier of 29.3 kcal mol. The first transition state is shown to possess diradical character linking the far peroxide oxygen to the bridging, reacting, peroxide oxygen. The energy of this first step, when calculated using hybrid density functional theory, is shown to depend heavily on the amount of Hartree-Fock exchange in the functional, with higher amounts leading to a higher barrier and more diradical character. Additionally, high amounts of spin contamination cause CCSD(T) to significantly overestimate the TS1 barrier with a value of 36.2 kcal mol when using the stable UHF wavefunction as the reference wavefunction. However, when using the restricted Hartree-Fock reference wavefunction, the TS1 CCSD(T) energy is lowered to yield a barrier of 31.2 kcal mol, in much better agreement with the NEVPT2 result. The second step in the reaction is the isomerization of HNO to trans-HONO through a Grotthuss-like mechanism accepting a proton from and donating a proton to the endogenous water. This new mechanism for the isomerization of HNO is shown to have an NEVPT2 barrier of 23.3 kcal mol, much lower than previous unimolecular estimates not including an explicit water. Finally, inclusion of an additional explicit water is shown to lower the HNO isomerization barrier even further.