Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces

Abstract

Terpyridine-substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl-crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn(2+) ions allowed for layer-by-layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid-state dye-sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed.

Building Up Colors: Multilayered Arrays of Peryleneimides on Flat Surfaces and Mesoporous Layers

“…Additionally, we synthesized the new 1,7‐di‐substituted perylene monoimide monoanhydride (PMIMA) 15 , working as an anchor group by opening the anhydride cycle and being immobilized onto the surface (Scheme ). 1,6‐Disubstituted PMI monoanhydride 16 described earlier was also used as an anchor element (Scheme ) …”

“…PMI diester 14 a was then hydrolyzed to anhydride 15 by using excess p TsOH in toluene, with further washing of the product with water until neutral pH to remove remaining p TsOH. The target compound 15 was obtained as a green solid in 93 % yield, after recrystallization and washing with n ‐pentane.…”

“…Initially, a quartz plate (QA1) covered with a 20 nm Al 2 O 3 layer on one side was used to build multilayers suitable for absorption, SEM, and X‐ray photoelectron spectroscopy (XPS) studies. Compound 16 (Scheme ), synthesized as reported earlier, was used as an anchor. The immobilization of 16 on substrates was performed through opening of the anhydride cycle.…”

“…Organic multilayers grafted on the solid surface can modify the interfacial properties; redox activity; photochemical responses; and electronic, optical, and charge‐transport mobility of the substrate . In our previous study, we demonstrated that terpyridinyl (tpy)‐substituted peryleneimides could form molecular arrays of significant length, not only in solutions, but also on solid substrates. The method is rather simple and straightforward and capable of producing highly ordered multilayered molecular films that might be beneficial for high‐tech applications.…”

Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

“…This dye was studied by femtosecond transient absorption spectroscopy, and results showed a slower charge recombination in the NDI-substituted complex. Perylene imides have been recently used by Sariola-Leikas et al [162] as bridge groups to obtain supramolecular structures for TiO 2 sensitization in solid state devices.…”