LUMO energies determination

The energy of the frontier orbitals determines the reactivity. The small energy gap between the HOMO of electron donors and the LUMO of electron acceptors promotes the interaction and stabilizes the transition states. Electron donors react fast as the HOMO energy is high. Electron acceptors reacts fast as the LUMO energy is low. 

The discovery of high conductivity in some organic compounds has initiated a whole era of research. The first and most used acceptor molecule is 7,7,8,8-tetracyanoquinomethane. A selenophene analog has been prepared starting from 2,5-dibromoselenophene (118) as shown in Eq. (41).151 Data for the solution electrochemistry and ESR spectroscopy of 119 and other acceptors containing dicyanomethylene units have been determined.152 In an attempt to correlate oxidation potentials with LUMO energies no obvious... 

AMI semi-empirical and B3LYP/6-31G(d)/AMl density functional theory (DFT) computational studies were performed with the purpose of determining which variously substituted 1,3,4-oxadiazoles would participate in Diels-Alder reactions as dienes and under what conditions. Also, bond orders for 1,3,4-oxadiazole and its 2,5-diacetyl, 2,5-dimethyl, 2,5-di(trifluoromethyl), and 2,5-di(methoxycarbonyl) derivatives were calculated <1998JMT153>. The AMI method was also used to evaluate the electronic properties of 2,5-bis[5-(4,5,6,7-tetrahydrobenzo[A thien-2-yl)thien-2-yl]-l,3,4-oxadiazole 8. The experimentally determined redox potentials were compared with the calculated highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) energies. The performance of the available parameters from AMI was verified with other semi-empirical calculations (PM3, MNDO) as well as by ab initio methods <1998CEJ2211>. 

Hexacyano[3]radialene (50) is a very powerful electron acceptor according to both experiment23,24 35 and MNDO calculations of LUMO energy and adiabatic electron affinity25. The easy reduction to the stable species 50" and 502- by KBr and Nal, respectively, has already been mentioned. Similarly, the hexaester 51 is reduced to 512-by Lil24. Most [3]radialenes with two or three quinoid substituents are reduced in two subsequent, well-separated, reversible one-electron steps. As an exception, an apparent two-electron reduction occurs for 4620. The reduction potentials of some [3]radialenes of this type, as determined by cyclic voltammetry, are collected in Table 1. Due to the occurrence of the first reduction step at relatively high potential, all these radialenes... 

While the reactivity is determined by the HOMO-LUMO energy separation, the selectivity is dominated by the orbital coefficients64. As a consequence, thekinetically controlled regioselectivity of the Diels-Alder ring closure, and thus the formation of the two new cr-bonds (between atoms 1,6 and 4,5 or between atoms 1,5 and 4,6 in Scheme 1), is determined by the FMO coefficients at the terminal carbon atoms of the diene and the dienophile. The FMO predictions boil down to the fact that the formation of cr-bonds between carbon atoms with similar orbital coefficients is preferred. The magnitudes of these coefficients... 

The rate-determining step of the DISPl mechanism, the protonation of the radical anion, largely depends on its electronic structure. As a guideline, LUMO energies of the parent hydrocarbon may... 

This assessment may be based on the so-called empirical resonance energies determined from thermodynamic parameters of reactions characterized by retention of structural type or on various indices of structural stability and reactivity, such as the HOMO-LUMO energy gap. 

The essential features of the Diels-Alder reaction are a four-electron n system and a two-electron it system which interact by a HOMO-LUMO interaction. The Diels-Alder reaction uses a conjugated diene as the four-electron n system and a it bond between two elements as the two-electron component. However, other four-electron it systems could potentially interact widi olefins in a similar fashion to give cycloaddition products. For example, an allyl anion is a four-electron it system whose orbital diagram is shown below. The symmetry of the allyl anion nonbonding HOMO matches that of the olefin LUMO (as does the olefin HOMO and the allyl anion LUMO) thus effective overlap is possible and cycloaddition is allowed. The HOMO-LUMO energy gap determines the rate of reaction, which happens to be relatively slow in this case. 

Cyclic voltammetry studies showed the ionization potential and electron affinity of each component of the molecule in solution. The HOMO and LUMO energy levels were estimated from the equations Ehomo = E x + 4.4 eV and Elumo = T 14+4.4 eV, where E(r]x and E%, were oxidation and reduction potentials with respect to the standard hydrogen electrode (SHE) and the value of 4.4 is the ionization potential for hydrogen in eV [94,95], The HOMO and LUMO energy levels of the methine dye (compound 6) (Scheme 13) were determined to be -5.82 and -3.48 eV, respectively, with respect to the vacuum level from... 

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