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The spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In thiswork, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociation of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl. [ABSTRACT FROM AUTHOR]

Huisgen's 1960 announcement of the concept of 1,3‐dipolar cycloadditions was published the year before Alder's study of the reaction of diazomethane and dimethylfulvene. The diazomethane reaction was studied again in 1970 by Houk et al. and shown to give a [6+4] adduct. Padwa's nitrile ylide cycloaddition to dimethylfulvene (1978) gave [6+4] and [4+2] adducts. We performed computational studies of these reactions with density functional theory (DFT) and show that they involve ambimodal [6+4]/[4+2] transition states that can lead to either type of cycloadduct from one transition state. We dedicate this paper to the extraordinary life and humanity of Rolf Huisgen, and to the undying influence of his discoveries on chemistry. [ABSTRACT FROM AUTHOR]

In this work, the aromatic hydroxylation mechanism of the [Cu2(H-XYL)O2]2+ complex mediated by a peroxo dicopper core and Cu-ligand effects are investigated by using hybrid density functional theory (DFT) and the broken symmetry B3LYP method. Based on the calculated free-energy profiles, we proposed two available mechanisms. The first reaction steps of both mechanisms involve concerted O--O bond cleavage and C--O bond formation and the second step involves the Wagner--Meerwein rearrangement of the substrate by a [1,2] H shift (HA shift from CA to CC) or (HA shift from CA to OA) across the phenyl ring to form stable dienone intermediates, and this is followed by the protonation of bridging oxygen atoms to produce the final hydroxylated dicopper(II) product. The HA shift from CA to CC mechanism is the energetically most favorable, in which the first reaction step is the rate-limiting reaction, with a calculated free-energy barrier of 19.0 kcal mol-1 and a deuterium kinetic isotope effect of 1.0, in agreement with experimental observations. The calculation also shows that the reaction started from the Ptype species of [Cu2(H-XYL)O2]2+ which is capable of mediating the direct hydroxylation of aromatic substrates without the intermediacy of an O-type species. Finally, we designed some new complexes with different Cu-ligands and found the complex that computationally possesses a higher activity in mediating the hydroxylation of the ligand based aromatic substrate; here, Cu loses a pyridyl ligand donor by dissociation, compared to the [Cu2(H-XYL)O2]2+ complex. [ABSTRACT FROM AUTHOR]

The unexpected formation of a 4-hydroxytetrahydroquinolin-2(1H)-one from a bicyclo[3.3.1]nonanetrione system and an amino alcohol in the presence of TsOH is reported. The mechanism of this transformation was studied by DFT calculations. The reaction provides an entry to the synthesis of highly functionalized 4-hydroxytetrahydroquinolin-2(1H)-ones. [ABSTRACT FROM AUTHOR]

A series of polyisocyanoprismanes, C6H6− n (NC) n (n =1–6), has been designed computationally. We have calculated the heats of formation (HOFs) of the title compounds by using density functional theory (DFT) with 6-31G** basis set. We chose [3]prismane C6H6-D 3h as a reference compound in the process of designing isodesmic reactions. The relationship between the HOFs and the molecular structures is discussed. The results have shown that the HOFs of the title compounds gradually increase with increasing number of isocyano groups. On average, the contribution of one isocyano group to the heat of formation is about 232.3kJ/mol and 234.1kJ/mol at the B3LYP and B3P86 levels, respectively. The relative stabilities of the title compounds are discussed in terms of the calculated HOFs, the energy gaps between the frontier orbitals, and the bond dissociation energies. The interactions of the isocyano groups in these polyisocyanoprismanes are also discussed. The results have not only shown that these compounds may be used as high-energy-density materials, but also provide some useful information for further syntheses. [Copyright &y& Elsevier]

A series of Ag(I) coordination oligomers with Ag-Ag distances tuned by amine auxiliary ligands were designed and synthesized. Their dual emissions could be adjusted by changing either excitation energy or temperature. The emission assignments were clarified by both experimental and DFT evidence herein. [ABSTRACT FROM AUTHOR]

The properties of synthesized ambipolar organic semiconductor (OSC) materials, containing hydrogen bonding, i.e. the 6,6′-dibromoindigo and the three s-indaceno [1, 2-b:5, 6-b′] dithiophene-4,9-dione derivatives, have been systematically studied using a density functional theory. The hydrogen bonding formed between the interlayer molecules, though it does not affect the charge mobility in the same layer, influences the interorbital overlapping of HOMO and LUMO states between the layers, and influences the charge mobility directly. In addition, the hydrogen bonding between the layers may reinforce the π-π stacking and make the center-to-center distance closer, which indirectly enhances charge mobility, and can turn a monopole OSC into an ambipolar one. [ABSTRACT FROM AUTHOR]

A series of phenyl end-capped derivatives of benzo[d,d′]thieno[3,2-b;4,5- b′]dithiophene (BTDT) with periphery-fluorinated substitutions (PFS) were systematically investigated by using density functional theory (DFT) combined with the Marcus–Hush electron transfer theory. The substituting effects of PFS were discussed. Compared with the original compounds, (i) the PFS compounds have a relatively higher efficiency of charge transport, lower barriers of electron injection, and larger HOMO-LUMO gaps; (ii) the air-stability and the device performance are enhanced by PFS; and (iii) the HOMO-LUMO transitions in the absorption spectrum of the PFS compounds show an obvious blue-shift trend. The perfluorophenylbisbenzo[d, d′]thieno[3,2-b;4,5-b′]dithiophene (BpF-BTDT) is found to be the most stable and most effective compound in charge transport among the investigated compounds, and it is suggested as an ambipolar semiconducting material. The results of electronic coupling of the bisbenzo[d, d′]thieno[3,2-b; 4,5- b′]dithiophene (BBTDT) derivatives show that the orbital interaction is mainly contributed by the neighboring molecule in the two dimensional (2D) layer. The PFS compounds have lower oxidization potential, ionization potential, and electron affinity values than the corresponding original ones, which suggest that fluorination can enhance the performance of the thiophene-based organic solar cells. These findings provide a better understanding of the PFS effects on organic semiconductors and may help to design high-performance semiconductor materials. [ABSTRACT FROM AUTHOR]

The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition. [ABSTRACT FROM AUTHOR]

Se--N dynamic covalent bond is a new dynamic covalent bond which has applications in the fabrication of stimuli responsive and self-healing functional materials. Although recent advances have been achieved in the experimental aspect, little is known about the formation mechanism of Se--N dynamic covalent bond. Here the structures and nature of Se--N dynamic covalent bond between three kinds of pyridine derivatives R-C5H4N, [pyridine (R = H), 4-methylpyridine (R = CH3), 4-dimethylamino-pyridine (R = N(CH3)2)] and phenylselenyl bromine (PhSeBr) have been analyzed using density functional theory. The interactions between Se atom in PhSeBr and N atom in pyridine or pyridine derivatives can be divided into three models: dissociation, nonbonding interaction and covalent bond interaction. Quantum chemical calculations on three series compounds show that these three models can convert mutually, which results in the generation of Se--N dynamic covalent bond. Solvent effects produced in polar solvents such as CH2Cl2 can make the conversion between Se--N covalent bond and Se...N nonbonding interactions easier. The kind of the substituents in pyridine ring can affect the conversion process: the stronger the electron-donating ability of the substituent, the easier the structure transformation. [ABSTRACT FROM AUTHOR]

Redox-active organic molecules have attracted much attention as alternatives to transition-metal-based electrodes for lithium-ion batteries due to their low cost and large abundance. However, the relatively low cycling stability still prevents some of the most promising molecules to be used as lithium-ion electrodes. Herein, we used 1,4,5,8-naphthalene diimide (NDI) as a model molecule to systematically investigate its intrinsic electrochemical property, including its electrolyte compatibility, maximum capacity, cycling stability, and rate capability in different organic electrolytes. Extensive physicochemical characterization, electrochemical measurement, and density function theory (DFT) calculation together show that the electrode-electrolyte interaction is the key factor determining its specific capacity and cycling stability. With a proper selection of electrolytes, NDI molecule, which was considered to be not stable for lithium storage, can achieve near theoretical capacity (based on two-electron reaction), very high rate capability, and high cycling stability. This study suggests the importance of understanding the fundamental electrode-electrolyte interactions in designing high-performance organic electrodes. [ABSTRACT FROM AUTHOR]