1394958-95-2Relevant academic research and scientific papers
Carbo-cyclohexadienes vs. carbo-benzenes: Structure and conjugative properties
Rives, Arnaud,Baglai, Iaroslav,Barthes, Ccile,Maraval, Valrie,Saffon-Merceron, Nathalie,Saquet, Alix,Voitenko, Zoia,Volovenko, Yulian,Chauvin, Remi
, p. 1139 - 1149 (2015/02/05)
Ideally Cs-/C2v-symmetric chromophores, constituted by two electro-active groups conjugated through the carbo-mer of the cyclohexa-1,3-diene core, are selectively prepared by the SnCl2-mediated reduction of tailored hexaoxy-[6]pericyclynes: in the latter substrates, one of the 1,4-dioxybut-2-yne edges is "chemically locked" by two CF3 substituents preventing complete reduction to the corresponding aromatic carbo-benzenic core, which is expected to be more "π-insulating" between the electro-active ends. The bis-trifluoromethylated carbo-cyclohexadiene products are also shown to be significantly stabilized with respect to their bis-phenylated analogues. Their structural (crystal X-ray diffraction analyses), spectroscopical (NMR and UV-vis spectra), physio-optical (dichromism in solution) and electrochemical (cyclic voltammograms) properties are compared on the basis of the electron-donating/electron-withdrawing nature of the substituents. These properties are also compared with those of their aromatic carbo-benzene and flexible carbo-n-butadiene counterparts.
Functional carbo-butadienes: Nonaromatic conjugation effects through a 14-Carbon, 24-p-electron backbone
Rives, Arnaud,Maraval, Val-Rie,Saffon-Merceron, Nathalie,Chauvin, Remi
, p. 483 - 492 (2014/04/03)
A systematic study of carbo-butadiene motifs not embedded in an aromatic carbo-benzene ring is described. Dibutatrienylacetylene (DBA) targets R 1-C(R)=C=C=C(Ph)- C=C-C(Ph)=C=C=C(R)-R2 are devised, in which R is C=CSiiPr3 and R1 and R2 are R, H, or 4-X-C6H4, with the latter including three known representatives (X: H, NMe 2, or NH2). The synthesis method is based on the SnCl 2-mediated reduction of pentaynediols prepared by early or late divergent strategies; the latter allows access to a OMe-NO2 push-pull diaryl-DBA. If R1 and R2 are H, an over-reduced dialkynylbutatriene (DAB) with two allenyl caps was isolated instead of the unsubstituted DBA. If R1=R2=R, the tetraalkynyl-DBA target was obtained, along with an over-reduced DBA product with a 12-membered 1,2-alkylidene-1H2,2H2-carbo-cyclobutadiene ring. X-ray crystallography shows that all of the acyclic DBAs adopt a planar trans-transoid-trans configuration. The maximum UV/Vis absorption wavelength is found to vary consistently with the overall p-conjugation extent and, more intriguingly, with the p-donor character of the aryl X substituents, which varies consistently with the first (reversible) reduction potential and first (irreversible) oxidation peak, as determined by voltammetry.
Highly π electron-rich macro-aromatics: Bis(p-aminophenyl)-carbo- benzenes and their DBA acyclic references
Rives, Arnaud,Baglai, Iaroslav,Malytskyi, Volodymyr,Maraval, Valerie,Saffon-Merceron, Nathalie,Voitenko, Zoia,Chauvin, Remi
, p. 8763 - 8765 (2012/10/08)
A series of stable quadrupolar bis(p-aminophenyl)-carbo-benzenes, featuring both donor-donor-donor π-frustration and central macro-aromaticity, is described and compared to the acyclic dibutatrienylacetylene (DBA) reference series.
