Design of N-N ylide bond-based high energy density materials: a theoretical survey.

The generally encountered contradiction between large energy content and stability poses great difficulty in designing nitrogen-rich high-energy-density materials. Although N-N ylide bonds have been classified as the fourth type of homonuclear N-N bonds (besides >N-N<, -N[double bond, length as m-dash]N-, and N[triple bond, length as m-dash]N), accessible energetic molecules with N-N ylide bonds have rarely been explored. In this study, 225 molecules with six types of novel structures containing N-N ylide bonds were designed using density functional theory and CBS-QB3 methods. To guide future synthesis, the effects of substitution on the thermal stability, detonation velocity, and detonation pressure of the structures were evaluated under the premise that the N-N ylide skeleton remains stable. The calculations show that the bond dissociation energy values of the N-N ylide bonds of the designed 225 structures were in the range of 61.21-437.52 kJ mol-1, except for N-1NNH2. Many of the designed structures with N-N ylide bonds exhibit high detonation properties, which are superior to those of traditional energetic compounds. This study convincingly demonstrates the feasibility of the design strategy of introducing an N-N ylide bond to develop new types of energetic materials.

Molecular design of D-π-A-π-D small molecule donor materials with narrow energy gap for organic solar cells applications.

CONTEXT: Developing novel materials present a great challenge to improve the photovoltaic performance of organic solar cells (OSCs). In this paper, we designed a series of the donor-π bridge-acceptor-π bridge-donor (D-π-A-π-D) structure molecules. These molecules consist of diketopyrrolopyrrole (DPP) moiety as core, 9-hexyl-carbazole moiety as terminal groups, and different planar electron-rich aromatic groups as π-bridges. The density functional theory (DFT) and time-dependent DFT (TD-DFT) computations showed that the frontier molecular orbital (FMO) energy levels, energy gaps, electron-driving forces (ΔEL-L), open-circuit voltage (Voc), fill factor (FF), reorganization energy (λ), exciton binding energy (Eb), and absorption spectra of the designed molecules can be effectively adjusted by the introduction of different π-bridges. The designed molecules have narrow energy gap and strong absorption spectra, which are beneficial for improving the photoelectric conversion efficiency of organic solar cells. In addition, the designed molecules possess large ΔEL-L, large Voc, and FF values and low Eb when the typical fullerene derivatives are used as acceptors. The FMO energy levels of the designed molecules can provide match well with the typical fullerene acceptors PC61BM, bisPC61BM, and PC71BM. Our results suggest that the designed molecules are expected to be promising donor materials for OSCs. METHODS: All DFT and TD-DFT calculations were carried out using the Gaussian 09 code. The computational technique chosen was the hybrid functional B3LYP and the 6-31G(d,p) basis set. The benzene and chloroform solvent effects have been considered using the polarized continuum model (PCM) at the TD-DFT level. The simulated absorption spectra of designed molecules were plotted by using the GaussSum 1.0 program.

Rational Design of π-Conjugated Tricoordinated Organoboron Derivatives With Thermally Activated Delayed Fluorescent Properties for Application in Organic Light-Emitting Diodes.

A series of donor-acceptor (D-A) tricoordinated organoboron derivatives (1-10) have been systematically investigated for thermally activated delayed fluorescent (TADF)-based organic light-emitting diode (OLED) materials. The calculated results show that the designed molecules exhibit small singlet-triplet energy gap (ΔE ST) values. Density functional theory (DFT) analysis indicated that the designed molecules display an efficient separation between donor and acceptor fragments because of a small overlap between donor and acceptor fragments on HOMOs and LUMOs. Furthermore, the delayed fluorescence emission color can be tuned effectively by introduction of different polycyclic aromatic fragments in parent molecule 1. The calculated results show that molecules 2, 3, and 4 possess more significant Stokes shifts and red emission with small ΔE ST values. Nevertheless, other molecules exhibit green (1, 7, and 8), light green (6 and 10), and blue (5 and 9) emissions. Meanwhile, they are potential ambipolar charge transport materials except that 4 and 10 can serve as electron and hole transport materials only, respectively. Therefore, we proposed a rational way for the design of efficient TADF materials as well as charge transport materials for OLEDs simultaneously.

A kinetically persistent isomer found for pentazole: a global potential energy surface survey.

Among the N5R family, pentazoles (A1) with a 103-year-old research history remain the only class of kinetically persistent isomers. Aided by the first global isomeric survey and substitution study of N5H at the composite CBS-QB3 level, we predicted a new N5R isomer (C1) with kinetic stability close to pentazoles.

Global Isomeric Survey of Elusive Cyclopropanetrione: Unknown but Viable Isomers.

Despite the great interest in energy storage application, stable neutral CnOn (n > 1) structures either in thermodynamics or kinetics have yet been largely limited due to the rather high tendency to release the very stable CO molecule. The neutral cyclopropanetrione (C3O3) cluster has long remained elusive since no isomer with sufficient kinetic stability has been found either experimentally or theoretically. In this work, we constructed the first global potential energy surface of singlet C3O3 at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level, from which the kinetic stability of a wide range of C3O3 isomers can be determined by investigating their isomerization and fragmentation pathways. Amongst, a three-membered ring structure 01 is the global C3O3 isomer with a barrier of 10.6 kcal/mol at the sophisticated W1BD level. In particular, two carbene-type isomers 02 and 04 possess appreciable destruction barriers of 20.3 and 24.7 kcal/mol at W1BD, respectively. Thus, 02 and 04 can be useful building blocks for constructing larger high-energy density carbon-oxygen clusters. Moreover, with the carbene center, both might effectively functionalize various nano-materials while retaining the electrochemical active carbonyl and epoxyl moieties that are very desirable in alkali metal-ion batteries.