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J Phys Chem B. 2013 May 2;117(17):5338-44. doi: 10.1021/jp312714x. Epub 2013 Apr 22.

Controlled fabrication and optoelectrical properties of metallosupramolecular films based on ruthenium(II) phthalocyanines and 4,4'-bipyridine covalently anchored on inorganic substrates.

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1
College of Materials Science and Engineering, Beijing Institute of Technology, 5 South Zhongguancun Street, Beijing, 100081, China. tongbin@bit.edu.cn

Abstract

Fully conjugated metallosupramolecular self-assembled multilayer films were controllably fabricated based on bibenzonitril-phthalocyaninato ruthenium(II) (BBPR) and 4,4'-bipyridine (BP) via axially coordination interaction between ruthenium ions and the pyridine groups on the modified substrates. The substrates were first functionalized by 4-(pyridine-4-ylethynyl)benzenic diazonium salt (PBD) through photodecomposition of diazonium group under UV irradiation. As a result, the pyridine-containing functional groups were vertically and covalently anchored onto the surface of substrate and got a stable monolayer. Soluble ruthenium phthalocyanine, axially coordinated by labile benzonitrile groups, was used to fabricate the layer-by-layer self-assembled films with BP through ligand-exchanging reaction between benzonitrile and pyridine in each self-assembled cycle. The UV-vis analysis results demonstrated the successful fabrication of bi(4,4'-bipyridine)phthalocyaninato ruthenium(II) (BPPR) metallosupramolecular ultrathin films with definite structures on PBD-modified substrate. Under illumination, the BPPR self-assembled multilayer films displayed a quick response to light. The maximum current density reached 120 nA/cm(2) at six bilayers. The Eg, HOMO, and LUMO of the six-bilayer were quantitatively measured to be 1.68, -5.29, and -3.61 eV, respectively. This strategy supplies a facile method to get full-conjugated metallosupramolecules and a platform for developing higher performance solar cell from the point of adjusting dye aggregate state structure.

PMID:
23570368
DOI:
10.1021/jp312714x
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