Materiais moleculares funcionais contendo n-heterociclos - capes

2858 R. Cristiano et al. / Tetrahedron 63 (2007) 2851–2858122.8, 126.4, 130.0, 131.5, 132.1, 132.6, 132.7, 153.5, 154.5,155.9, 164.1, 164.5. Elemental analysis for C 66 H 66 N 4 O 10 ,calcd: C, 73.72; H, 6.19; N, 5.21. Found: C, 73.67; H,6.19; N, 5.09%.4.7.2. 2,3-Dicyano-5,6-bis-4-[4-(3,4,5-tridodecyloxybenzoyloxy)benzoyloxy]phenylpyrazine (15). Yellow solid.Yield: 70%; T g 32 C. IR (film) n max cm 1 : 2923, 2853,2358 (C^N, weak), 1737 (C]O), 1594, 1502, 1462, 1431,1380, 1335, 1261, 1164, 1061. 1 H NMR (CDCl 3 ) d ppm:0.88 (m, 18H, CH 3 ), 1.26–1.49 (broad, 108H, –CH 2 –),1.75–1.86 (m, 12H, CH 2 CH 2 O–), 4.05 (t, 12H, –CH 2 O–),7.32 (d, J¼8.4 Hz, 4H, Ar–H), 7.37 (d, J¼8.8 Hz, 4H, Ar–H), 7.41 (s, 4H, Ar–H), 7.70 (d, J¼8.8 Hz, 4H, Ar–H),8.28 (d, J¼8.4 Hz, 4H, Ar–H). 13 C NMR (CDCl 3 ) d ppm:14.4, 22.9, 26.3, 29.5, 29.6, 29.9, 30.0, 30.6, 32.1, 69.5,73.9, 108.8, 113.3, 122.5, 122.7, 123.4, 126.6, 130.0, 131.6,132.2, 132.8, 143.6, 153.3, 153.5, 154.5, 155.8, 164.0, 164.7.Elemental analysis for C 118 H 170 N 4 O 14 , calcd: C, 75.84; H,9.17; N, 3.00. Found: C, 75.78; H, 9.11; N, 3.09%.4.7.3. 2,3-Dicyano-5,6-bis-4-[3,4,5-tris-(4-dodecyloxybenzyloxy)benzoyloxy]phenylpyrazine (16). Yellowsolid. Yield: 59%; mp 92.9–96.0 C. IR (film) n max cm 1 :2923, 2856, 1721 (C]O), 1593, 1508, 1464, 1428, 1380,1244, 1183, 1111. 1 H NMR (CDCl 3 ) d ppm: 0.88 (m,18H, CH 3 ), 1.26–1.44 (br, 108H, –CH 2 –), 1.78 (br, 12H,CH 2 CH 2 O–), 3.92–3.96 (m, 12H, –CH 2 O–), 5.04 and 5.07(2 s, 12H, ArCH 2 O–), 6.76 (d, J¼8.4 Hz, 4H, Ar–H), 6.89(d, J¼8.4 Hz, 8H, Ar–H), 7.25–7.28 (m, 8H overlappedwith CDCl 3 signal, Ar–H), 7.33 (d, J¼8.4 Hz, 8H, Ar–H),7.49 (s, 4H, Ar–H), 7.68 (d, J¼8.4 Hz, 4H, Ar–H). 13 CNMR (CDCl 3 ) d ppm: 14.4, 22.9, 26.3, 29.6, 29.7, 29.9,32.1, 68.3, 71.4, 75.0, 110.0, 113.3, 114.4, 114.7, 114.9,122.8, 123.7, 128.5, 129.5, 130.2, 130.5, 131.5, 132.7,143.7, 153.0, 153.6, 154.5, 159.3, 164.5. Elemental analysisfor C 146 H 198 N 4 O 16 , calcd: C, 77.41; H, 8.81; N, 2.47. Found:C, 76.93; H, 9.05; N, 2.16%.AcknowledgementsThe authors thank Dr. Frank Quina from Universidade deS~ao Paulo (USP) and Dr. Faruk Nome from UniversidadeFederal de Santa Catarina (UFSC) for the free access tothe photophysical equipment, the Laboratorio de SistemasNanoestruturados (LabSiN) for the film deposition, and tothe Laboratorio de Filmes Finos e Superfıcies (LFFS) forthe AFM facilities, both located at Departamento de Fısica,UFSC. The authors thank Dr. Andre A. Pasa for helpfuldiscussions. This work was supported by Conselho Nacionalde Desenvolvimento Cientıfico e Tecnologico (CNPq,Brazil), FAPESC (Brazil), FINEP (Brazil), and Merck(Germany).Supplementary dataThe complete set of the 1 H and 13 C NMR, UV–vis and fluorescencespectra in solid phase, as well as DSC and TGAcurves of the new compounds are available. Supplementarydata associated with this article can be found in the onlineversion, at doi:10.1016/j.tet.2007.01.045.References and notes1. (a) Shirota, Y. J. Mater. 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