Directional electron and hole transport is essential in photosynthesis. Applied to molecular optoelectronics such as organic solar cells, these lessons from nature call for oriented supramolecular n/p-heterojunctions (SHJs) that contain various chromophores and antiparallel redox gradients (OMARGs). In this tutorial review, we summarize recent progress made toward the construction of OMARG-SHJs. This conceptually innovative twist added to a timely topic should appeal to the synthetic organic, supramolecular, biological, physical, analytical and materials chemist as well as to the expert in energy and environmental sciences.
Lessons from nature call for supramolecular n/p-heterojunctions with oriented multicolored antiparallel redox gradients (OMARG-SHJs) as "ideal" photosystems. Their design combines advantages of bilayer and bulk n/p-heterojunction (BHJ) solar cells for the directional separation of photogenerated charges before recombination can occur. Although conceptually attractive, OMARG-SHJs have remained beyond reach because of unresolved challenges in synthetic organic and supramolecular chemistry. Here we report the first OMARG-SHJs with two-component redox gradients in both the electron- and hole-transporting pathways. They were obtained by zipper assembly of stacks of red naphthalenediimide (NDI) electron donors along strings of oligophenylethynyl hole acceptors on top of yellow NDI electron acceptors along p-oligophenyl hole donors. The presence of both gradients is shown to be essential for achieving photoinduced charge separation over very long distances.
Matching matters when building supramolecular n/p‐heterojunction photosystems on solid supports that excel with efficient photocurrent generation, important critical thickness, smooth surfaces, and flawless responsiveness to functional probes for the existence of operational intra‐ and interlayer recognition motifs.
A new synthetic route to prepare a series of versatile 2,7-substituted pyrene synthons for the synthesis of pyrene-fused azaacenes is described. By using such synthons, a library of eight pyrene-fused azacenes with different electronic structures and in most cases with enhanced solubility has been synthesized and characterized.
We investigated the synthesis of one-dimensional nanostructures via Schiff base (imine) formation on three close-packed coinage metal (Au, Ag, and Cu) surfaces under ultrahigh vacuum conditions. We demonstrate the feasibility of forming pyrene-fused pyrazaacene-based oligomers on the Ag(111) surface by thermal annealing of tetraketone and tetraamine molecules, which were designed to afford cyclocondensation products. Direct visualization by scanning tunneling microscopy of reactants, intermediates, and products with submolecular resolution and the analysis of their statistical distribution in dependence of stoichiometry and annealing temperature together with the inspection of complementary X-ray photoelectron spectroscopy signatures provide unique insight in the reaction mechanism, its limitations, and the role of the supporting substrate. In contrast to the reaction on Ag(111), the reactants desorb from the Au(111) surface before reacting, whereas they decompose on the Cu(111) surface during the relevant thermal treatment.
Diverse supramolecular assemblies ranging from nanometres to micrometers of small aromatic π-conjugated functional molecules have attracted enormous research interest in light of their applications in optoelectronics, chemosensors, nanotechnology, biotechnology and biomedicines. Here we study the mechanism of the formation of a flower-shaped supramolecular structure of phosphonic acid appended naphthalene diimide with melamine. The flower-shaped assembly formation was visualised by scanning electron microscope (SEM) and transmission electron microscopy (TEM) imaging, furthermore, XRD and DLS used to determined mode of aggregation. Characteristically, phosphonic acid-substituted at imide position of NDIs possess two important properties resulting in the formation of controlled flower-like nanostructures: (i) the aromatic core of the NDI which is designed to optimize the dispersive interactions (π-π stacking and van der Waals interactions) between the cores within a construct and (ii) phosphonic acid of NDI interact with malamine through molecular recognition i.e. strong hydrogen-bonding (H-bonding). We believe such arrangements prevent crystallization and favour the directional growth of flower-like nanostructure in 3D fashion. These works demonstrate that complex self-assembly can indeed be attained through hierarchical non-covalent interactions of two components. Furthermore, flower-like structures built from molecular recognition by these molecules indicate their potential in other fields if combined with other chemical entities.
Supramolecular self-assembly and self-organization are simple and convenient ways to design and create controlled assemblies with organic molecules, and they have provoked great interest due to their potential applications in various fields, such as electronics, photonics, and light-energy conversion. Herein, we describe the synthesis of two π-conjugated porphyrin molecules bearing tetraphenylethene moieties with high fluorescence quantum yield. Photophysical and electrochemical studies were conducted to understand the physical and redox properties of these new materials, respectively. Furthermore, these derivatives were used to investigate self-assembly via the solvophobic effect. The self-assembled aggregation was performed in nonpolar and polar organic solvents and forms nanospheres and ring-like nanostructures, respectively. The solution based aggregation was studied by means of UV-vis absorption, emission, XRD, and DLS analyses. Self-assembled ring-shape structures were visualized by SEM and TEM imaging. This ring-shape morphology of nanosized macromolecules might be a good candidate for the creation of artificial light-harvesting nanodevices.
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