Full-conjugated Layer-by-Layer self-assembly Ultrathin Functional Films Fabricted from Terpyridine and Transition Metal Ions based on Coordinate Interaction

Abstract

A novel conjugated light-sensitive diazonium-containing compound, 4'-(2,2':6',2''-terpyridyl) benzenediazonium tetrafluoroborate (Diazo-tpy) was firstly synthesized and used to modify substrate by electrostatic interaction. Following the decomposition of diazonium group of Diazo-tpy under UV irradia-tion, the ionic bonds between the diazonium salt and substrate are converted to the covalent bonds. The ter-pyridine-containing monolayer film anchoring on the substrate is very stable. Specially, the π-conjugated system of the terpyridinyl groups is linked to the surface of the substrate, which can greatly facilitate the transport of charges between them. Furthermore, the layer-by-layer (LBL) self-assembled (SA) films of 4'?4'''-(1,4-phenyl)-bis(2,2':6',2''-terpyridine) (Bi-tpy) and different transition metal ions (Pt4+、Ru3+、Rh3+、Pd2+) were fabricated on the tpy-modified substrate, and were well characterized using UV-vis absorption spectroscopy. The UV-vis analytic results indicate that the LBL Bi-tpy/Mtn+ SA multilayer films, having axial ligand between metal atom and terpyridyl group, have been successfully fabricated and a pro-gressive assembly runs regularly with almost equal amount of deposition in each cycle. Under illumination, the SA films on ITO shows an effective photoinduced charge transfer and changed the current density of the ITO. The result revealed that the photoelectric conversion property of Bi-tpy/Ru film is higher than that of Bi-tpy/Pt film. With an increase in the layer number, the photocurrent rises and reaches its maximum at 6 bilayers. Further increment leads to a current drop due to the increase in probability of objection and the cell resistance. The results allow us to design new materials for more optoelectronic applications.

Key words: terpyridine, transition metal ion, layer-by-layer self-assembly, coordinate interaction, photoelectric property

Cite this article

BO Ru-Xiu, TONG Bin, QI Dun-Ge, DIAO Wei, SHEN Jin-Bei, DAN Jian-Bing, DONG Yu-Beng. Full-conjugated Layer-by-Layer self-assembly Ultrathin Functional Films Fabricted from Terpyridine and Transition Metal Ions based on Coordinate Interaction[J]. Acta Chimica Sinica, 2009, 67(24): 2779-2784.

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References

1 (a) Iler, R. K. J. Colloid Interface Sci. 1966, 21, 569.
(b) Zhang, X.; Chen, H.; Zhang, H.-Y. Chem. Commun.
2007, 1395.
2 (a) Decher, G.; Hong, J. D. Makromol. Chem. Macromol.
Symp. 1991, 46, 321.
(b) Decher, G. Science 1997, 277, 1232.
3 (a) Sun, J.; Wu, T.; Sun, Y.-P.; Wang, Z.; Zhang, X.; Shen,
J.-C.; Cao, W.-X. Chem. Commun. 1998, 1853.
(b) Bai, S.; Lu, C.-H.; Cao, W.-X. Acta Chim. Sinica 2005,
63(9), 866 (in Chinese).
(白硕, 鲁从华, 曹维孝, 化学学报, 2005, 63(9), 866.)
(c) Cao, T.-B.; Wei, L.-H.; Yang, S.-M.; Zhang, M.-F.;
Huang, C.-H.; Cao, W.-X. Langmuir 2002, 18, 750.
(d) Yao, G.-J.; Dong, Y.-P.; Cao, T.-B.; Yang, S.-M.; Yip, J.
L. W.; Tang, B.-Z. J. Colloid Interface Sci. 2003, 257, 263.
(e) Zhi, J.-G.; Tian, X.-L.; Zhao, W.; Shen, J.-B.; Tong, B.;
Dong, Y.-P. J. Colloid Interface Sci. 2008, 319, 270.
2784 化学学报 Vol. 67, 2009
4 (a) Yin, H.-Z.; Liu, H.; Li, Y.-Y.; He, X.-W.; Chen, L.-X.;
Li, W.-Y. Acta Chim. Sinica 2005, 63(8), 734 (in Chinese).
(尹洪宗, 刘辉, 李园园, 何锡文, 陈朗星, 李文友, 化学
学报, 2005, 63(8), 734.)
(b) Wang, Y.-Y.; Ma, Z.; Wang, P.; Huang, W. Acta Chim.
Sinica 2007, 65(18), 2057 (in Chinese).
(王嬿嬿, 马谆, 王培, 黄维, 化学学报, 2007, 65(18),
2057.)
(c) Ogura, R. Y.; Nakane, S.; Morooka, M.; Orihashi, M.;
Suzuki, Y.; Noda, K. Appl. Phys. Lett. 2009, 94, 073308.
5 (a) Lee, H.; Kepley, L. J.; Hong, H. G.; Mallouk, T. E. J.
Am. Chem. Soc. 1988, 110, 618.
(b) Lee, H.; Kepley, L. J.; Hong, H. G.; Akhter, S.; Mallouk,
T. E. J. Phys. Chem. 1988, 92, 2597.
6 Xiong, H. M.; Cheng, M. H.; Zhou, Z.; Zhang, X.; Shen, J.
C. Adv. Mater. 1998, 10, 529.
7 Zhao, W.; Tong, B.; Pan, Y.-X.; Shen, J.-B.; Zhi, J.-B.; Shi,
J.-B.; Dong, Y.-P. Langmuir 2009, 25, 11796.
8 Morgan, G. T.; Burstall, F. H. J. Chem. Soc. Abstr. 1932, 20.
9 Newkome, G. R.; Wang, P. S.; Moorefield, C. N.; Cho, T. J.;
Mohapatra, P. P.; Li, S. N.; Hwang, S. H.; Lukoyanova, O.;
Echegoyen, L.; Palagallo, J. A.; Iancu, V.; Hla, S. W. Science
2006, 312, 1782.
10 Kosbar, L.; Srinivasan, C.; Afzali, A. Langmuir 2006,
22(18), 7631.
11 (a) Kristi, O.; McLaughlin, R. L.; Williams, M. E. Inorg.
Chem. 2007, 46(3), 965.
(b) Poddutoori, P. K.; Poddutoori, P.; Maiya, B. G.; Prasad,
T. K.; Kandrashkin, Y. E.; Vasilev, S.; Bruce, D. Inorg.
Chem. 2008, 47(17), 7512.
12 (a) Shunmugam, R.; Tew, G. N. Chem. Eur. J. 2008, 14(13),
5409.
(b) Kadjane, P.; Charbonnière, L.; Ziessel, R. J. Fluoresc.
2008, 18(1), 119.
13 Padhi, S. K.; Saha, D.; Manivannan, V.; Subramanian, J.;
Manivannan, V. Polyhedron 2008, 27(6), 1714.
14 (a) Lin, X. F.; Phillips, D. L. J. Org. Chem. 2008, 73(10),
3680.
(b) Du, P. W.; Schneider, J.; Fan, L.; Zhao, W.; Patel, U.;
Castellano, F. N.; Eisenberg, R. J. Am. Chem. Soc. 2008,
130(15), 5056.
(c) Gnanamgari, D.; Crabtree, R. H. Organometallics 2009,
28(3), 922.
15 (a) Chen, H. Y.; Tagore, R.; Olack, G.; Vrettos, J. S.; Weng,
T. C.; Penner-Hahn, J.; Crabtree, R. H.; Brudvig, G. W.
Inorg. Chem. 2007, 46(1), 34.
(b) Wang, H.-T.; Hu, T.-T.; Zhang, Q.-L.; Liu, J.-H.; Ren,
X.-Z.; Li, C.-H.; Wang, F.; Zhang, P.-X. Acta Chim. Sinica
2008, 66(13), 1565 (in Chinese).
(王海滔, 胡婷婷, 张黔玲, 刘剑洪, 任祥忠, 李翠华, 王
芳, 张培新, 化学学报, 2008, 66(13), 1565.)
(c) Corral, E.; Hotze, A. C. G.; Dulk, H. D.; Leczkowska,
A.; Rodger, A.; Hannon, M. J.; Reedijk, J. J. Biol. Inorg.
Chem. 2009, 14, 439.
16 (a) Schütte, M.; Kurth, D. G.; Linford, M. R. Angew. Chem.,
Int. Ed. 1998, 37(1), 20.
(b) Caruso, F.; Schuler, C.; Kurth, D. G. Chem. Mater. 1999,
11, 3394.
(c) Kurth, D. G.; Severin, N.; Rabe, J. P. Angew. Chem., Int.
Ed. 2002, 41(19), 3681.
(d) Kurth, D. G.; Meister, A.; Thunemann, A. F.; Forster, G.
Langmuir 2003, 19(10), 4055.
(e) Bodenthin, Y.; Pietsch, U.; Grenzer, J.; Geue, T.;
Mohwald, H.; Kurth, D. G. J. Phys. Chem. B 2005, 109(26),
12795.
17 (a) Maskus, M.; Abruna, H. D. Langmuir 1996, 12, 4455.
(b) Yamanoi, Y.; Nishihara, H. Chem. Commun. 2007, 3983.
18 Kosynkin, D. V.; Tour, J. M. Org. Lett. 2001, 3(7), 993.
19 Ng, W. Y.; Gong, X.; Chan, W. K. Chem. Mater. 1999, 11,
1165.
20 (a) Cheng, K. W.; Chan, W. K. Langmuir 2005, 21, 5247.
(b) Gao, L.-L.; Tong, B.; Yao, G.-J.; Dong, Y.-P.; Zhang,
M.-F.; Lam Jacky, W.-Y.; Tang, B.-Z. Acta Polymerica
Sinica 2005, (3), 313 (in Chinese).
(高玲玲, 佟斌, 姚桂君, 董宇平, 张茂锋, Lam Jacky W.
Y., 唐本忠, 高分子学报, 2005, (3), 313.)
21 Newkome, G. R.; Cho, T. J.; Moorefield, C. N.; Cush, R.;
Russo, P. S.; Godinez, L. A.; Saunders, M. J.; Mohapatra, P.
Chem. Eur. J. 2002, 8(13), 2946.
22 Gil, L.; Moraga, E.; Bunel, S. Mol. Phys. 1967, 12, 333.
23 Pramanik, P.; Bag, N. J. Chem. Soc., Dalton Trans. 1992,
(1), 97.

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