Synthesis of Chromophore Core Frechet-Type Dendrimer by Oxidative Homo-Coupling of Terminal Alkyne

Seung Choul Han; Tae Gyu Song; Sung-Ho Jin; Jae Wook Lee

Macromolecular Research, Vol.29, No.6, 430-434, June, 2021

DOI10.1007/s13233-021-9051-2 Export Citation

Synthesis of Chromophore Core Frechet-Type Dendrimer by Oxidative Homo-Coupling of Terminal Alkyne

Seung Choul Han, Tae Gyu Song, Sung-Ho Jin^{1, †}, and Jae Wook Lee^†

Department of Chemistry, Dong-A University, Busan 49315, Korea
¹Department of Chemistry Education, Pusan National University, Busan 46241, Korea

E-mail:,

The alkyne-functionalized Frechet-type dendrons 2-Dm containing benzamine were synthesized by N-alkylation of the corresponding dendritic benzyl chlorides with 4-ethynylaniline. The oxidative homo-coupling reaction of the alkynefunctionalized Frechet-type dendrons 2-Dm was allowed to provide the first through fourth generation dendrimers 3-Gm with 1,4-diphenylbuta-1,3-diynes at chromophore core in high yields. Their structure of dendrimers was confirmed by 1H and 13C NMR spectroscopy, IR spectroscopy, mass spectrometry, and GPC analysis. The photophysical properties of the synthesized dendrimers was investigated.

Keywords:alkyne;1,3-diyne;dendrimer;homo-coupling;light-harvesting

[References]

Lo SC, Burn PL, Chem. Rev., 107(4), 1097 (2007)
(a) Jiang DL, et al., Nature, 388, 454 (1997). (b) Jiang DL, Aida T, J. Am. Chem. Soc., 120, 10895 (1998). (c) Sato T, et al., J. Am. Chem. Soc., 121, 10658 (1999). (d) Freeman AW, et al., J. Am. Chem. Soc., 122, 12385 (2000). (e) Nantalaksakul A, et al., Photosynth. Res., 87, 133 (2006).
Kobayashi M, Machida S, Takahashi S, Horie K, Yoshikawa H, Masuhara H, Chem. Lett., 31(3), 394 (2002)
a)Astruc D, et al., Chem. Rev., 110, 1857 (2010). (b) Paolucci V, et al., J. Phys. Chem. B, 120, 9576 (2016). (c) Caminade AM, et al., Chem. Eur. J., 15, 9270 (2009). (d) Augustus EN, et al., J. Polym. Sci., 7, 8 (2017).
Adronov A, Frechet JMJ, Chem. Commun., 1701 (2000).
Hwang SH, Moorefield CN, Newkome GR, Chem. Soc. Rev., 37, 2543 (2008)
Lo SC, Burn PL, Chem. Rev., 107(4), 1097 (2007)
Burn PL, Lo SC, Samuel IDW, Adv. Mater., 19(13), 1675 (2007)
(a) Newkome GR, et al., Dendrimers and Dendrons: Concepts, Synthesis, Applications, Wiley-VCH, Weinheim, 2001. (b) Frechet JMJ, Tomalia DA, Dendrimers and Other Dendritic Polymers, John Wiely & Sons Ltd., Chichester, 2002.
Diederich F, Stang PJ, Eds. In Metal-Catalyzed Crosscoupling Reactions, Wiley-VCH, Weinheim, 1998
(a) Tour JM, Chem. Rev., 96, 537 (1996). (b) Martin RE, Diederich F, Angew. Chem. Int. Ed., 38, 1350 (1999).
Yamaguchi M, Park HJ, Hirame M, Torisu K, Nakamura K, Minami T, Nishihara H, Hiraoka T, Bull. Chem. Soc. Jpn., 67, 1717 (1994)
Lehn JM, Supramolecular Chemistry: Concepts and Perspectives, VCH, Weinheim, 1995.
(a) Lee JW, et al., Bull. Korean Chem. Soc., 30, 1925 (2009). (b) Han SC, et al., Bull. Korean Chem. Soc., 32, 3899 (2011).
Lee JW, Han SC, Kim HJ, Kim JH, Lee UY, Kim BK, Sung SR, Kang HS, Kim JH, Huh DS, Polym. Korea, 31(5), 417 (2007)

[1] Lo SC, Burn PL, Chem. Rev., 107(4), 1097 (2007)

[2] (a) Jiang DL, et al., Nature, 388, 454 (1997). (b) Jiang DL, Aida T, J. Am. Chem. Soc., 120, 10895 (1998). (c) Sato T, et al., J. Am. Chem. Soc., 121, 10658 (1999). (d) Freeman AW, et al., J. Am. Chem. Soc., 122, 12385 (2000). (e) Nantalaksakul A, et al., Photosynth. Res., 87, 133 (2006).

[3] Kobayashi M, Machida S, Takahashi S, Horie K, Yoshikawa H, Masuhara H, Chem. Lett., 31(3), 394 (2002)

[4] a)Astruc D, et al., Chem. Rev., 110, 1857 (2010). (b) Paolucci V, et al., J. Phys. Chem. B, 120, 9576 (2016). (c) Caminade AM, et al., Chem. Eur. J., 15, 9270 (2009). (d) Augustus EN, et al., J. Polym. Sci., 7, 8 (2017).

[5] Adronov A, Frechet JMJ, Chem. Commun., 1701 (2000).

[6] Hwang SH, Moorefield CN, Newkome GR, Chem. Soc. Rev., 37, 2543 (2008)

[7] Lo SC, Burn PL, Chem. Rev., 107(4), 1097 (2007)

[8] Burn PL, Lo SC, Samuel IDW, Adv. Mater., 19(13), 1675 (2007)

[9] (a) Newkome GR, et al., Dendrimers and Dendrons: Concepts, Synthesis, Applications, Wiley-VCH, Weinheim, 2001. (b) Frechet JMJ, Tomalia DA, Dendrimers and Other Dendritic Polymers, John Wiely & Sons Ltd., Chichester, 2002.

[10] Diederich F, Stang PJ, Eds. In Metal-Catalyzed Crosscoupling Reactions, Wiley-VCH, Weinheim, 1998

[11] (a) Tour JM, Chem. Rev., 96, 537 (1996). (b) Martin RE, Diederich F, Angew. Chem. Int. Ed., 38, 1350 (1999).

[12] Yamaguchi M, Park HJ, Hirame M, Torisu K, Nakamura K, Minami T, Nishihara H, Hiraoka T, Bull. Chem. Soc. Jpn., 67, 1717 (1994)

[13] Lehn JM, Supramolecular Chemistry: Concepts and Perspectives, VCH, Weinheim, 1995.

[14] (a) Lee JW, et al., Bull. Korean Chem. Soc., 30, 1925 (2009). (b) Han SC, et al., Bull. Korean Chem. Soc., 32, 3899 (2011).

[15] Lee JW, Han SC, Kim HJ, Kim JH, Lee UY, Kim BK, Sung SR, Kang HS, Kim JH, Huh DS, Polym. Korea, 31(5), 417 (2007)