Comparative studies on rigid π linker-based organic dyes: Structure-property relationships and photovoltaic performance

© 2014 Wiley-VCH Verlag GmbH & Co. KGaA. A series of six structurally correlated donor-π bridge-acceptor organic dyes were designed, synthesized, and applied as sensitizers in dye-sensitized solar cells. Using the most widely studied donor (triarylamine) and cyclopenta[1,2-b:5,4-b′]dithiophene or cyclopenta[1,2-b:5,4-b′]dithiophene[2′,1′:4,5]thieno-[2,3-d]thiophene as π spacers, their structure-property relationships were investigated in depth by photophysical techniques and theoretical calculations. It was found that the photovoltaic performance of these dyes largely depends on their electronic structures, which requires synergistic interaction between donors and acceptors. Increasing the electron richness of the donor or the elongation of π-conjugated bridges does not necessarily lead to higher performance. Rather, it is essential to rationally design the dyes by balancing their light-harvesting capability with achieving suitable energy levels to guarantee unimpeded charge separation and transport

Rodlike Bimetallic Ruthenium and Osmium Complexes Bridged by Phenylene Spacers. Synthesis, Electrochemistry, and Photophysics.

In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2′-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 Å for the shortest and longest complex, respectively. For one of the ruthenium precursors, [RUbpy-ph2-Si(CH3) 3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed

Organic semi-conducting architectures for supramolecular electronics

The properties of organic electronic materials in the solid-state are determined not only by those of individual molecules but also by those of ensembles of molecules. The ability to control the architectures of these ensembles is thus essential for optimizing the properties of conjugated materials for use in electronic devices (light emitting diodes, field effect transistors, solar cells, …) and is primordial for potential technological applications in nanoelectronics. Here, we report on the observation by atomic force microscopy (AFM) of 1D and 2D nanoscale architectures obtained in the solid-state from solutions of molecularly-dissolved conjugated block copolymers or oligomers, and demonstrate that the conjugated molecules can organize onto a surface over lengthscales from nanometers to several microns, forming semiconducting fibrils or bi-dimensional organizations (monolayers) by p-stacking processes (by changing the sample preparation conditions)

One and Two-Dimensional Semiconducting Nanostructures Self-Assembly of Conjugated Oligomers

The properties of organic electronic materials in the solid-state are determined not only by those of individual molecules but also by those of ensembles of molecules. The ability to control the architectures of these ensembles is thus essential for optimising the properties of conjugated materials for use in electronic devices (light emitting diodes, field effect transistors, solar cells,…) and is primordial for potential technological applications in nanoelectronics. Here, we report on the observation by atomic force microscopy (AFM) of 1D and 2D nanoscale architectures obtained in the solid-state from solutions of molecularly-dissolved conjugated block copolymers or oligomers, and demonstrate that the conjugated molecules can organize onto a surface over lengthscales from nanometers to several microns, forming semiconducting fibrils by π-stacking processes

One and two-dimensional semiconducting nanostructures self-assembly of conjugated oligomers

The properties of org. electronic materials in the solid-state are detd. not only by those of individual mols. but also by those of ensembles of mols. The ability to control the architectures of these ensembles is thus essential for optimizing the properties of conjugated materials for use in electronic devices (light emitting diodes, field effect transistors, solar cells, ...) and is primordial for potential technol. applications in nanoelectronics. Here, we report on the observation by at. force microscopy (AFM) of 1D and 2D nanoscale architectures obtained in the solid-state from solns. of molecularly-dissolved conjugated block copolymers or oligomers, and demonstrate that the conjugated mols. can organize onto a surface over lengthscales from nanometers to several microns, forming semiconducting fibrils by p-stacking processe