Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Abstract

Two donor-σ-acceptor molecules containing tetrathiafulvalene (TTF) and carbazole moieties were synthesized by the reaction of 9-(4-bromo-butyl)-carbazole (1) with 2,6-bis(hexylthio)-3-(2-cyanoethylthio)-7-(methylthio)-tetrathiafulvalene (2) or 2,6-bis(2-cyanoethylthio)-3,7-bis(methylthio)tetrathiafulvalene (3) in the presence of CsOH·H₂O, respectively. The structures of the molecules were characterized by ¹H NMR, ¹³C NMR, MS, and elemental analyses. They showed negligible intramolecular charge-transfer interaction in their ground states as indicated by their UV-Vis spectroscopics and cyclic voltammetry results. Compared with carbazole, their fluorescence was strongly quenched, which implied that a photo induced electron transfer (PET) interaction between TTF and carbazole moieties occurred.

Keywords

donor-σ-acceptor molecule / intramolecular charge transfer interaction / photo induced electron transfer / tetrathiafulvalene / carbazole

References

[1] Aviram A, Ratner M. Molecular rectifiers. Chem Phys Lett, 1974, 29: 277-286

[2] Khodorkovsky V, Becker J Y. In Organic Conductors: Fundamentals and Applications. New York: Matcel Dekker, 1994, 75-88

[3] Marder S R, Kippelen B, Jen A K Y, Peyghambarian N. Design and synthesis of chromophores and polymers for electro-optic and photorefractive applications. Nature, 1997, 388: 845-851

[4] Imahori H, Sakata Y. Donor-linked fullerenes: photoinduced electron transfer and its potential application. Adv Mater, 1997, 9: 537-546

[5] Bryce M R. Tetrathiafulvalenes as π-electron donors for intramolecular charge-transfer materials. Adv Mater, 1999, 11: 11-23

[6] Tsiperman E, Regev L, Becher J Y, Bernstein J, Ellern A, Khodorkovsky V, Shames A, Shapiro L. Synthesis of a novel rigid tetrathiafulvalene-s-p-benzoquinone diad (TTF-σ-Q) with inherent structural configuration suitable for intramolecular charge-transfer. Chem Commun, 1999, 1125-1126

[7] Nielsen M B, Hansen J G, Becher J. Self-complexing tetrathiafulvalene-based donor-acceptor macrocycles. Eur J Org Chem, 1999, 2807-2815

[8] Sadaike S I, Takimiya K, Aso Y, Otsubo T. TTF-porphyrin dyads as novel photoinduced electron transfer systems. Tetrahedron Lett, 2003, 44: 161-165

[9] Martín N, Sánchez L, Herranz M A, Guldi D M. Evidence for two separate one-electron transfer events in excited fulleropyrrolidine dyads containing tetrathiafulvalene (TTF). J Phys Chem A, 2000, 104: 4648-4657

[10] Simonsen K B, Zong K, Rogers R D, Cava M P, Becher J. Stable macrocyclic and tethered donor-acceptor systems: intramolecular bipyridinium and tetrathiafulvalene assemblies. J Org Chem, 1997, 62: 679-686

[11] Li S F, Zhong G Y, Zhu W H, Li F Y, Pan J F, Huang W, Tian H. Dendritic europium complex as single dopant for white-light electroluminescent device. J Mater Chem, 2005, 15: 3221-3228

[12] Tabei E, Fukushima M, Mori S. Conductivity of doped N-carbazolyl-substituted polysilanes. Synth Met, 1995, 73: 113-116

[13] Chun H, Moon I K, Shin D H, Kim N. Preparation of highly efficient polymeric photorefractive composite containing an isophorone-based NLO chromophore. Chem Mater, 2001, 13: 2813-2817

[14] Lee J H, Park J W, Choia S K. Synthesis and electroluminescent property of a new conjugated polymer based on carbazole derivative: poly(3,6-N-2-ethylhexyl carbazolyl cyanoterephthalidene). Synth Met, 1997, 88: 31-35

[15] Simonsen K B, Svenstrup N, Lau J, Simonsen O, MΦrk P, Kristensen G J, Becher J. Sequential functionalisation of bis-protected tetrathiafulvalene-dithiolates. Synthesis, 1996, 3: 407-418

[16] Miguel P, Bryce M R, Goldenberg L M, Beeby A, Khodorkovsky V, Shapiro L, Niemz A, Cuello A O, Rotello V. Synthesis and intramolecular charge-transfer properties of new tetrathiafulvalene-tetracyanoanthraquinodimethane diad (TTF–σ-TCNAQ) and triad (TTF–σ-TCNAQ–σ-TTF) molecules. J Mater Chem, 1998, 8: 71-76

[17] Bang K S, Nielsen M B, Zubarev R, Becher J. Tetrathiafulvalene-phenanthroline macrocycles as redox responsive sensors for metal ions. Chem Commun, 2000, 215-216

[18] Zhang G X, Zhang D Q, Guo X F, Zhu D B. A new redox-fluorescence switch based on a triad with tetrathiafulvalene and anthracene units. Org Lett, 2004, 6: 1209-1212

[19] Flood A H, Nygaard S, Laursen B W, Jeppesen J O, Stoddart J. Locking down the electronic structure of (monopyrrolo)tetrathiafulvalene in [2] rotaxanes. Org Lett, 2006, 8: 2205-2208

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