MACROCYCLIC TETRAETHYNYLETHENE MOLECULAR SCAFFOLDING - PERETHYNYLATED AROMATIC DODECADEHYDRO[18]ANNULENES, ANTIAROMATIC OCTADEHYDRO[12]ANNULENES, AND EXPANDED RADIALENES

Tetraethynylethene (3,4-diethynylhex-3-ene-1,5-diyne) molecular scaffolding provided access to novel macrocyclic nanometer-sized C-rich molecules with unusual structural and electronic properties. Starting from cis-bis-deprotected cis-bis(trialkylsilyl)-protected tetraethynylethenes, the per(silylethynyl)ated octadehydro[12]annulenes 1 and 2 and the corresponding dodecadehydro[18]annulenes 4 and 5 were prepared by oxidative Hay coupling. X-Ray crystal-structure analyses of (i-Pr)(3)Si-protected 2 and Me(3)Si-protected 4 showed that both annulene perimeters are perfectly planar. Electronic absorption spectral comparisons provided strong evidence that the macro rings in the deep-purple-colored 1 and 2 are antiaromatic (4n pi-electrons), whereas those in yellow 4 and 5 are aromatic ((4n + 2) pi-electrons). Although unstable in solution, the antiaromatic compound 2 gave high-melting crystals in which the individual octadehydro[12]annulene chromophores are isolated and stabilized in a matrix-type environment formed by the bulky (i-Pr)(3)Si groups. Electrochemical studies demonstrated that the antiaromatic octadehydro[12]annulene 2 undergoes two stepwise one-electron reductions more readily than the aromatic chromophore 5. This redox behavior is best explained by the formation of an aromatic (4n + 2) pi-electron dianion from 2, whereas 5 loses its aromaticity upon reduction. The Me,Si derivative 4 was deprotected with borax in MeOH/THF to give the highly unstable hexaethynyl-dodecadehydro[18]annulene 6, a C30H6 isomer and macrocyclic precursor to a two-dimensional all-C-network. Deprotection of 2 did not give isolable amounts of tetraethynyl-octadehydro[12]annulene 3 due to the extreme instability of the latter. Starting from dimeric and trimeric acyclic tetraethynylethene oligomers, a series of expanded radialenes were obtained. They possess large C-cores with silylethynyl-protected peripheral valences and can be viewed as persilylated C-40 (7), C-50 (8), and C-60 (9) isomers. These expanded C-sheets are high-melting, highly stable, soluble materials which were readily characterized by laser-desorption time-of-night (LD-TOF) mass spectrometry. Due to inefficient macrocyclic cross-conjugation and/or non-planarity, the extent of pi-electron delocalization in 7-9 is limited to the longest linearly conjugated pi-electron fragment. In agreement with these properties, all three expanded radialenes exhibited similar redox behavior; they are difficult to oxidize but undergo several reversible one-electron reductions in similar potential ranges. Presumably, the reduced pi-electron delocalization is also at the origin of the particularly high stability of 7-9.