SYNTHESIS AND CHARACTERIZATION OF NOVEL 4-CYNANOPHENYLFUNCTIONALIZED N4,N4,N4′,N4′-TERAPHENYLBENZIDINE (TPB) AS HOLE TRANSPORTING MOLECULAR MATERIALS

Abstract

In this study, a new cyanophenyl-functionalized N4,N4,N4′,N4′-tetraphenylbenzidine (TPB) containing employable hole-transporting components has been synthesized with Pd-catalyzed Suzuki-Miyaura cross coupling reaction. N4,N4,N4′,N4′tetrakis-(4′-cynobiphenyl-4-yl)-biphenyl-4,4′-diamine (TPB-CN)  was well characterized by 1H NMR, 13C NMR and CHN elemental analysis. The compound TPB-CN exhibited good thermal stability and luminescence properties. Time Dependent Density Functional Theory (TDDFT) computation was carried out to investigate the structural parameters and to understand the photophysical properties of the novel TPB-CN compound. The experimental and theoretical calculations performed to calculate absorption maxima in DCM by UV-Vis and TD-B3LYP/6-31g(d,p) were compared with each other. To identify crystal structure and to determine optical band gap of TPB-CN compound, its film form, which was coated on the glass substrate by spin coating, was used. The band gap of TPB-CN compound both in film and in solution was determined from the optical absorption measurements.

Keywords

• N4N4N4′N4′-tetraphenylbenzidine (TPB)
• Suzuki-Miyaura cross-coupling
• Organic semiconductor
• TDDFT

References

1. [1] Klauk H, Organic Electronics, Manufacturing and Applications. ed. Wiley-VCH: Weinheim, 2006.
2. [2] Klauk H, Organic Electronics II: More Materials and Applications. ed. Wiley-VCH, Weinheim, 2012
3. [3] Facchetti A., Mater. Today A. Facchetti., Mater Today, 2007; 10: 28-37.
4. [4] Shirota Y, Kageyama H, Charge Carrier Transporting Molecular Materials and Their Applications in Devices. Chem Rev 2007; 107: 953-1010.
5. [5] Meng Q, Dong H L, Hu W, Zhu D, Recent progress of high performance organic thin film field-effect transistors. J Mater Chem 2011; 21: 11708-11721.
6. [6] Hagfeldt A, Boschloo G, Sun L, Kloo L, Pettersson H, Dye-Sensitized Solar Cells Chem. Rev. 2010; 110: 6595-6663.
7. [7] Saragi T P I, Fuhrmann-Lieker T, Salbeck J, Comparison of Charge-Carrier Transport in Thin Films of Spiro-Linked Compounds and Their Corresponding Parent Compounds Adv Funct Mater 2006; 16: 966-974.
8. [8] Kawamura Y, Yamaoto H, Goushi K, Sasabe H, Yoshizaki H, Ultraviolet amplified spontaneous emission from thin films of 4,4′-bis(9-carbazolyl)-2,2′-biphenyl 4,4′-bis(9-carbazolyl)-2,2′-biphenyl and the derivatives Appl Phys Lett 2004; 84: 2724-2726.

9. [9] F´aber R, Mielke G F, Rapta P, Stasko A, Nuyken O, Anodic Oxidation of Novel Hole-Transporting Materials Derived from Tetraarylbenzidines. Electrochemical and Spectroscopic Characterization Collect Czech Chem Commun 2000; 65: 1403-1418.
10. [10] Yokozumi T, Miyashita Y, Hayashi K, Ogino K, Usui H, Gonda M, Sato H, Fabrication and characteristics of hole transporting materials–transition metal nanoparticle composites Thin Solid Films 2004; 449: 173-179.
11. [11] Heun S, Borsenberger P M, Hole transport in triarylamine doped polymers Physica B Condensed Matter 1995; 216: 43-52.
12. [12] Shen Y L, Diest K, Wong M H, Hsieh B R, Dunlap D H, Malliaras G G, Charge transport in doped organic semiconductors Phys Rev B 2003; 68: 081204-081208.
13. [13] Yuan W, Gong Y, Chen S, Shen X,. Lam J W Y, Lu P, Lu Y, Wang Z, Hu R, Xie N, Kwok H.S, Zhang Y, Sun J, Tang B, Efficient Solid Emitters with Aggregation-Induced Emission and Intramolecular Charge Transfer Characteristics: Molecular Design, Synthesis, Photophysical Behaviors, and OLED Application Chem Mater 2012; 24: 1518-1528.
14. [14] Miyaura N, Suzuki A, Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds Chem Rev 1995; 95: 2457-2483.
15. [15] Suzuki A, In Metal-Catalysed Cross-Coupling Reactions Diederich, F., Stang, P. J. eds. Wiley-VCH: Weinheim, 1997.
16. [16] Hall, D., Boronic Acids. ed. Wiley VCH: Weinheim, 2005.
17. [17] Spencer J, Baltus C B, Patel H, Press N J, Callear S K, Male L, and Coles S J, Microwave-mediated synthesis of an arylboronate library ACS Comb Sci 2011; 13: 24-31.
18. [18] Molander A G, Traister K M, Barcellos T, Palladium-Catalyzed α-Arylation of 2-Chloroacetates and 2-Chloroacetamides J Org Chem 2013; 78: 4123-4131.
19. [19] Khedkar M V, Tambade P J, Qureshi Z S, Bhanage B M, Pd/C: An Efficient, Heterogeneous and Reusable Catalyst for Phosphane-Free Carbonylative Suzuki Coupling Reactions of Aryl and Heteroaryl Iodides Eur J Org Chem. 2010; 36: 6981-6986.
20. [20] Cao X, Wen Y, Guo Y, Yu G, Liu Y, Yang L, Undoped, red organic light-emitting diodes based on a N,N,N’,N’-tetraphenylbenzidine (TPD) derivative as red emitter with a triphenylamine derivative as hole-transporting layer Dyes and Pigments, 2010; 84: 203-207.
21. [21] Bellman E, Shaheen S E, Grubbs R H, Marder S R, Kippelen, Peyghambarian N, Organic Two-Layer Light-Emitting Diodes Based on High-Tg Hole-Transporting Polymers with Different Redox Potentials Chem Mater 1999; 11: 399-407.
22. [22] Frisch M J, et al. Gaussian 09, Revision D,Gaussian, Inc., Wallingford, CT, 2010.
23. [23] Gapol M A B, Balanay M P, Kim D H, Molecular Engineering of Tetraphenylbenzidine-Based Hole Transport Material for Perovskite Solar Cell J. Phys. Chem. A 2017; 121: 1371−1380.
24. [24] Pankove J I, Optical Processes in Semiconductors, Prentice-Hall Inc., Englewoord Cliffs, NJ. 1971