Biradical molecules

Scheme 3 Chemical stmctures of neutral tc-radical and biradical molecules of organic conductors...

Using this switching unit, several biradical molecules were examined (see below). In the syntheses of these compounds, diiodo derivative 15 was used as... 

Magnetic susceptibilities of 10a and 10b were measured on a SQUID suscep-tometer in microcrystalline form. %T-T plots are shown in Fig. 9.5. The data were analyzed in terms of a modified singlet-triplet two-spin model (the Blea-ney-Bowers-type), in which two spins (S = V2) couple antiferromagnetically within a biradical molecule by exchange interaction J. The best-fit parameters obtained by means of a least-squares method were 2J/kB = -2.2 + 0.04 K for 10a and -11.6 + 0.4 K for 10b. Although the interaction (2J/kB = -2.2 K) between the two spins in the open-ring isomer 10a was weak, the spins of 10b showed a remarkable antiferromagnetic interaction (2J/kB = -11.6 K). 

Shimizu A, Kubo T, Uruichi M, Yakushi K, Nakano M, Shiomi D, Sato K, Takui T, Hirao Y, Matsumoto K, Kurata H, Morita Y, Nakasuji K (2010) Alternating covalent bonding interactions in a one-dimensional chain of a phenalenyl-based singlet biradical molecule having Kekule structures. J Am Chem Soc 132 14421-14428... 

Figure 12.22 Schematic illustration of Inequivalent dimers, A and B, in the low-temperature phase of the bIradIcal, m-BNN two oircles connected by a solid line denote a biradical molecule (S = 1). Lower part shows the spin configurations in these dimers. The configuration on the right-hand side corresponds to the thermally excited triplet state the ellipsoid represents the weak covalent-bond formation between the biradicals in dimer B.

An anchor, as defined above, contains stable molecules, conformers, all pairs of radicals and biradicals formed by a simple bond fission in which no spin re-pairing took place, ionic species, and so on. Figure 1 shows some examples of species belonging to the same anchor. Thus, an anchor is a more general and convenient temi used in the discussion of spin re-pairing. 

Molecules 1,4-CHDN 1,3-CHDN BCE benzene -I- H2 BCE/allyl biradical... 

The concept of biradicals and biradicaloids was often used in attempts to account for the mechanism of photochemical reactions [2,20,129-131]. A biradical (or diradical) may be defined as [132] an even-electron molecule that has one bond less than the number permitted by the standard rules of valence. 

For singlet spin molecules at the equilibrium geometry, RHF and UHF wave functions are almost always identical. RHF wave functions are used for singlets because the calculation takes less CPU time. In a few rare cases, a singlet molecule has biradical resonance structures and UHF will give a better description of the molecule (i.e., ozone). 

The problem of the synthesis of highly substituted olefins from ketones according to this principle was solved by D.H.R. Barton. The ketones are first connected to azines by hydrazine and secondly treated with hydrogen sulfide to yield 1,3,4-thiadiazolidines. In this heterocycle the substituents of the prospective olefin are too far from each other to produce problems. Mild oxidation of the hydrazine nitrogens produces d -l,3,4-thiadiazolines. The decisive step of carbon-carbon bond formation is achieved in a thermal reaction a nitrogen molecule is cleaved off and the biradical formed recombines immediately since its two reactive centers are hold together by the sulfur atom. The thiirane (episulfide) can be finally desulfurized by phosphines or phosphites, and the desired olefin is formed. With very large substituents the 1,3,4-thiadiazolidines do not form with hydrazine. In such cases, however, direct thiadiazoline formation from thiones and diazo compounds is often possible, or a thermal reaction between alkylideneazinophosphoranes and thiones may be successful (D.H.R. Barton, 1972, 1974, 1975). 

Closed-shell molecules have a multiplicity of one (a singlet). Arad-ical, with one unpaired electron, has a multiplicity of two (a doublet). A molecular system with two unpaired electrons (usually a triplet) has a multiplicity of three. In some cases, however, such as a biradical, two unpaired electrons may also be a singlet. 

By including electron correlation in the wave function the UHF method introduces more biradical character into the wave function than RHF. The spin contamination part is also purely biradical in nature, i.e. a UHF treatment in general will overestimate the biradical character. Most singlet states are well described by a closed-shell wave function near the equilibrium geometry, and in those cases it is not possible to generate a UHF solution which has a lower energy than the RHF. There are systems, however, for which this does not hold. An example is the ozone molecule, where two types of resonance structure can be drawn. Figure 4.8. 

Also in this case the relative energy of all the possible intermediates involved in the photochemical isomerization was calculated (OOOJOC2494). The results are collected in Fig. 2. Also in this case the sensitized irradiation involves the formation of the biradicals. We have to note, however, that the fission of O—Cq, bond in the triplet state of the molecule is not so favored as in furan. The process should be quite inefficient. The corresponding biradicals show the same energy as that in the triplet state. In this case, then, the formation of a biradical should depend on the activation energy. 

When the reaction was carried out on the phenoxy derivative 106, only 107 was obtained (Scheme 44) (88JHC1551). The formation of this product was rationalized assuming a heteroly tic cleavage of the O—N bond followed by isomerization (Scheme 44). If the reaction occurs in the excited triplet state of the molecule, the biradical is the most probable intermediate. 

The results described above represent the first example of the FR mechanism (Scheme 1). Semiempirical calculations on this molecule showed that the intersystem crossing to the excited triplet state is favored The reaction cannot be sensitized by xanthone because the triplet state of 3,4-diphenyl-1,2,5-oxadiazole is lower than that of xanthone. The cleavage of the triplet state to the biradical is favored, considering the relative energy of this intermediate (Fig. 23) (OOOUPl). 

The two most widely accepted mechanisms for the spontaneous generation of radicals from S are the biradical mechanism (top half of Scheme 3.61) first proposed by Flory314 and the Mayo315 or MAH (molecule assisted homolysis) mechanism (lower pari of Scheme 3.61). 

A biradical is a molecule with two unpaired electrons. The unpaired electrons are usually on different atoms, as depicted in (20). In that biradical, one unpaired electron is on one carbon atom of the chain and the second is on another carbon atom several bonds away. In some cases, though, both electrons are on the same atom. One of the most important examples is the oxygen atom itself. Its electron configuration is He]2s22/ x.22py12pzl and its Lewis symbol is -O. The O atom has two unpaired electrons, and so it can be regarded as a special type of biradical. 

This highly conjugated molecule was stabilised with nitroxyl biradical side chains. The resulting material had sufficient ferromagnetism that a usable compass needle could be made from it. Despite the success of this demonstration, organic ferromagnetism remains a curiosity. Such polymers are not likely to replace conventional ferromagnetic metals in any application within the foreseeable future. 

The dioxygen molecule exists in two forms a triplet or ground state in which it is a stable biradical and a singlet or excited state in which it is not a radical. Reactions of carotenoids with singlet oxygen have already been presented in this chapter and we now focus on the reactions of carotenoids and oxygen in the ground or triplet state. 

Photoelectron spectroscopy has routinely been used to determine the ionization energies of stable molecules. It has also been adapted for the investigation of reactive species, including radicals, biradicals, and carbenes, usually generated chemically or by using pyrolysis. ... 

Hehre and co-workers have used this approach for the investigation of biradicals and other reactive neutral molecules. For example, by using the bracketing approach, they were able to determine the proton affinities of o- and p-xylylene (o- and p-quinodimethane (lo and Ip) Figure 5.3), from which they were able to determine the enthalpies of formation of the reactive, Kekule molecules. They found the proton affinity of the meta isomer to be too high to be measured directly by bracketing, but were able to assign a lower limit, and subsequently a lower limit to the enthalpy of formation of the m-xylylene diradicals. 

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