Orientational Organization of Organic Semiconductors within Periodic Nanoscale Silica Channels: Modification of Fluorophore Photophysics through Hierarchical Self‐Assembly

Abstract

Smart nanomaterials: The orientational organization of small organic semiconductors (anthracene, in this case) within periodic nanoscale silica channels (see figure) is achieved through a novel hierarchical self-assembly approach. This elicits interesting optical effects and improved mechanical properties that could be of potential importance for functional materials.A novel hierarchical organic-inorganic self-assembly approach is proposed in driving the orientational organization of small organic semiconductors (anthracene, in this case). A cationic surfactant with the special organic semiconductor anthracene at the hydrophobic tail was synthesized and used as both the structure-directing agent and as functional nanobuilding blocks. The self-assembly procedure was rapid and allowed for the uniform and molecular-level controllable organization of the organic semiconductors within periodic nanoscale silica channels. A range of techniques were used to demonstrate that the photophysical and photochemical nature of anthracene is significantly altered in the inorganic host, consistent with orientational packing of the organic semiconductors and excimer formation within the channels, from which energy migration and significant emission occur. The nanocomposite has also been demonstrated to show an interesting selective sensor function with respect to small solvent molecules. We suggest that this method could be used to drive the assembly of a wide range of organic semiconductor guests, offering the development of a variety of useful, smart nanomaterials that are able to self-assemble in a controllable and robust fashion.

Functional-template directed self-assembly (FTDSA) of mesostructured organic-inorganic hybrid materials

“…Recent research has witnessed rapid advances in selfassembly as a most promising approach for the synthesis igure 6 Schematic illustration for the process of using the functional-template directed self-assembly to drive the assembly of an attached organic semiconductor, an anthracene in this case, to form locally ordered structures within the periodic nanoscale silica channels, for the modification of fluorophore photophysics [60] .…”

“…With the inspiration of such systems, the control of the supramolecular orientation and alignment has attracted considerable attention in the field of semiconductor materials for their electronic and optoelectronic applications. Most recently, we have developed the FTDSA approach in driving the orientational organization of organic semiconductors (anthracene, in this case) within the periodical nanoscale silica channels (Figure 6) [60] . In this approach, one cationic surfactant with an anthracene at the end of its hydrophobic tail is synthesized and used as both structure-directing agents and functional building blocks.…”

Synthesis and Luminescence Properties of Pomponlike CaMoO₄:Eu³⁺ Red Phosphors by Hydrothermal Method

“…Recently, syntheses of materials with specific morphologies and sizes have been attracting great interest because of their unique physical, chemical and biological properties and potential applications in advanced functional materials [1,2]. The self-assembly technique has been recognized as an important strategy for the exquisite fabrication of hierarchical constructions, because it can easily control the shape growth of materials hierarchical structures [3,4]. Many self-assembly processes are carried out under hydrothermal reaction conditions, especially assisted by using different organic reagents.…”

Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents

“…Detection techniques including optical absorption spectroscopy, quartz crystal microbalance (QCM), and FTIR have been utilized for aromatic hydrocarbon sensing applications based on these materials [4,9–18]. We have previously reported on the potential of mesoporous organosilicate materials for the semi-selective adsorption of targets [19,20].…”