Nanocage-Confined Synthesis of Fluorescent Polycyclic Aromatic Hydrocarbons in Zeolite

Abstract

Polycyclic aromatic hydrocarbons (PAHs) attract much attention for applications to organic light-emitting diodes, field-effect transistors, and photovoltaic cells. The current synthetic approaches to PAHs involve high-temperature flash pyrolysis or complicated step-by-step organic reactions, which lead to low yields of PAHs. Herein, we report a facile and scalable synthesis of PAHs, which is carried out simply by flowing acetylene gas into zeolite under mild heating, typically at 400 °C and generates the products of 0.30 g g zeolite. PAHs are synthesized via acetylene polymerization inside Ca-ion-exchanged Linde type A (LTA) zeolite, of which the α-cage puts a limit on the product molecular size as a confined-space nanoreactor. The resultant product after the removal of the zeolite framework exhibits brilliant white fluorescence emission in N-methylpyrrolidone solution. The product is separated into four different color emitters (violet, blue, green, and orange) by column chromatography. Detailed characterizations of the products by means of various spectroscopic methods and mainly mass spectrometric analyses indicate that coronene (CH) is the main component of the blue emitter, while the green emitter is a mixture of planar and curved PAHs. The orange can be attributed to curved PAHs larger than ovalene, and the violet to smaller molecules than coronene. The PAH growth mechanism inside Ca-exchanged LTA zeolite is proposed on the basis of mass spectral analyses and density functional theory calculations.

Electrochemiluminescence Enhanced by Restriction of Intramolecular Motions (RIM): Tetraphenylethylene Microcrystals as a Novel Emitter for Mucin 1 Detection

“…Over the past few years, the polycyclic aromatic hydrocarbons (PAHs) , have been considered to be a hot spot, because of their inexpensive production, structural tailorability, and excellent optoelectronic properties. These inherent superiorities drew tremendous interest for the potential applications of PAHs in diverse research fields such as advanced organic devices, biosensors, materials science, and asymmetric catalysis. − Among them, the electrochemiluminescence (ECL) properties of PAHs (such as 9,10-diphenylanthracene (DPA), perylene, rubrene (Rub), phenanthrene derivatives) − were particularly eye-catching, since the systemic study of ECL was reported in 1964 .…”

“…O ver the past few years, the polycyclic aromatic hydrocarbons (PAHs) 1,2 have been considered to be a hot spot, because of their inexpensive production, structural tailorability, and excellent optoelectronic properties. These inherent superiorities drew tremendous interest for the potential applications of PAHs in diverse research fields such as advanced organic devices, biosensors, materials science, and asymmetric catalysis.…”

Revival of Zeolite‐Templated Nanocarbon Materials: Recent Advances in Energy Storage and Conversion

“…When referring to zeolite-templated 3D porous carbons, the investigations from Ryoo et al cannot be ignored. [20,21,81,92,99,[230][231][232] Since 1990s, Ryoo et al synthesized and prepared a series of nanocarbon materials templated by zeolites. Massive efforts from Ryoo et al were invested to elucidate the effect of cations of zeolites in synthesis and preparation of nanocarbon materials, as shown in Figure 12.…”

“…cannot be ignored. [ 20,21,81,92,99,230–232 ] Since 1990s, Ryoo et al. synthesized and prepared a series of nanocarbon materials templated by zeolites.…”

Swing Arm Location-Controllable DNA Walker for Electrochemiluminescence Biosensing

“…Electrochemiluminescence (ECL) has aroused great interest by virtue of its high sensitivity, wide range, and low background signals. − Compared with traditional ECL emitters, such as luminol and Ru­(bpy) 3 2+ , polycyclic aromatic hydrocarbons (PAHs) and derivatives as ECL luminophores have received great attention for ECL bioanalysis and imaging over the past few decades due to their high fluorescence (FL) quantum efficiency, relatively low cost, and structural tailorability. − Perylene (Pe) is a PAH molecule with a large π-conjugated structure, which has been extensively explored owing to its excellent photochemical properties. However, the unexpected aggregation-caused quenching (ACQ) effect was unavoidable when it was in solid or aggregated states, because Pe as a typical plane molecule was prone to form aggregates via intermolecular π–π stacking, which will decrease their emission efficiency.…”