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Non-kekul MoleculeA non-Kekul molecule is a conjugated hydrocarbon that cannot be assigned classical Kekul structures. Since non-Kekul molecules have two or more formal radical centers, their spin-spin interactions can cause conductivity or ferromagnetism, and applications to functional materials are expected. However, as these molecules are quite reactive and most of them are easily decomposed or polymerized at room temperature, strategies for stabilization are needed for their practical use. Synthesis and observation of these reactive molecules are generally accomplished by matrix-isolation methods. Classification of non-Kekul molecules Non-Kekul molecules with two formal radical centers (non-Kekul diradicals) can be classified into non-disjoint and disjoint by the shape of their two non-bonding molecular orbitals (NBMOs). Both NBMOs of molecules with non-disjoint characteristics such as trimethylenemethane (TMM) have electron density at the same atom. According to Hund's rule, each orbital is filled with one electron with parallel spin, avoiding the Coulomb repulsion by filling one orbital with two electrons. Therefore, such molecules with non-disjoint NBMOs are expected to prefer a triplet ground state. In contrast, the NBMOs of the molecules with disjoint characteristics such as tetramethyleneethane (TME) can be described without having electron density at the same atom. With such MOs, the destabilization factor by the Coulomb repulsion becomes much smaller than with non-disjoint type molecules, and therefore the relative stability of the singlet ground state to the triplet ground state will be nearly equal, or even reversed because of exchange interaction. Non-Kekul molecules can also be classified by their structural characteristics. Non-Kekul polyenes are conjugated carbon chains such as TMM or TME. TMM was the first observed non-Kekul molecule found in 1966 by Paul Dowd. Non-Kekul quinodimethanes are biradicaloids of a six-membered ring with methylene substituents. Non-Kekul polynuclear aromatics are composed of several fused six-membered rings. The synthesis of Triangulene, the simplest non-Kekul polynuclear aromatic, was first tried by Eric Clar in 1953, but it was not even observed until the syntheses of trioxytriangulene by Richard J. Bushby in 1995 and kinetically stabilized triangulene by Kazuhiro Nakasuji in 2001.
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