Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

Metal-organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.

State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis.

Because of its fundamental importance in many branches of science, hydrogen bonding is a subject of intense contemporary research interest. The physical and chemical properties of hydrogen bonds in the ground state have been widely studied both experimentally and theoretically by chemists, physicists, and biologists. However, hydrogen bonding in the electronic excited state, which plays an important role in many photophysical processes and photochemical reactions, has scarcely been investigated.Upon electronic excitation of hydrogen-bonded systems by light, the hydrogen donor and acceptor molecules must reorganize in the electronic excited state because of the significant charge distribution difference between the different electronic states. The electronic excited-state hydrogen-bonding dynamics, which are predominantly determined by the vibrational motions of the hydrogen donor and acceptor groups, generally occur on ultrafast time scales of hundreds of femtoseconds. As a result, state-of-the-art femtos...

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Hydrogen Bonding in the Electronic Excited State

More than 95% (in volume) of all of today’s chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic rese...

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

Metal–organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and metal ions or clusters. High electrical conductivity is rare in M...

Electrically Conductive Metal-Organic Frameworks.

Organic semiconducting single crystals (OSSCs) are ideal candidates for the construction of high-performance optoelectronic devices/circuits and a great platform for fundamental research due to their long-range order, absence of grain boundaries, and extremely low defect density. Impressive improvements have recently been made in organic optoelectronics: the charge-carrier mobility is now over 10 cm2 V-1 s-1 and the fluorescence efficiency reaches 90% for many OSSCs. Moreover, high mobility and strong emission can be integrated into a single OSSC, for example, showing a mobility of up to 34 cm2 V-1 s-1 and a photoluminescence yield of 41.2%. These achievements are attributed to the rational design and synthesis of organic semiconductors as well as improvements in preparation technology for crystals, which accelerate the application of OSSCs in devices and circuits, such as organic field-effect transistors, organic photodetectors, organic photovoltaics, organic light-emitting diodes, organic light-emitting transistors, and even electrically pumped organic lasers. In this context, an overview of these fantastic advancements in terms of the fundamental insights into developing high-performance organic semiconductors, efficient strategies for yielding desirable high-quality OSSCs, and their applications in optoelectronic devices and circuits is presented. Finally, an overview of the development of OSSCs along with current challenges and future research directions is provided.

Organic Semiconductor Single Crystals for Electronics and Photonics.

Flexible electronics have attracted considerable attention recently given their potential to revolutionize human lives. High-performance organic crystalline materials (OCMs) are considered strong candidates for next-generation flexible electronics such as displays, image sensors, and artificial skin. They not only have great advantages in terms of flexibility, molecular diversity, low-cost, solution processability, and inherent compatibility with flexible substrates, but also show less grain boundaries with minimal defects, ensuring excellent and uniform electronic characteristics. Meanwhile, OCMs also serve as a powerful tool to probe the intrinsic electronic and mechanical properties of organics and reveal the flexible device physics for further guidance for flexible materials and device design. While the past decades have witnessed huge advances in OCM-based flexible electronics, this review is intended to provide a timely overview of this fascinating field. First, the crystal packing, charge transport, and assembly protocols of OCMs are introduced. State-of-the-art construction strategies for aligned/patterned OCM on/into flexible substrates are then discussed in detail. Following this, advanced OCM-based flexible devices and their potential applications are highlighted. Finally, future directions and opportunities for this field are proposed, in the hope of providing guidance for future research.

Organic crystalline materials in flexible electronics

The remarkable merits of 2D materials with atomically thin structures and optoelectronic attributes have inspired great interest in integrating 2D materials into electronics and optoelectronics. Moreover, as an emerging field in the 2D-materials family, assembly of organic nanostructures into 2D forms offers the advantages of molecular diversity, intrinsic flexibility, ease of processing, light weight, and so on, providing an exciting prospect for optoelectronic applications. Herein, the applications of organic 2D materials for optoelectronic devices are a main focus. Material examples include 2D, organic, crystalline, small molecules, polymers, self-assembly monolayers, and covalent organic frameworks. The protocols for 2D-organic-crystal-fabrication and -patterning techniques are briefly discussed, then applications in optoelectronic devices are introduced in detail. Overall, an introduction to what is known and suggestions for the potential of many exciting developments are presented.

2D Organic Materials for Optoelectronic Applications

A cocrystal strategy with a simple preparation process is developed to prepare novel materials for near-infrared photothermal (PT) conversion and imaging. DBTTF and TCNB are selected as electron donor (D) and electron acceptor (A) to self-assemble into new cocrystals through non-covalent interactions. The strong D–A interaction leads to a narrow band gap with NIR absorption and that both the ground state and lowest-lying excited state are charge transfer states. Under the NIR laser illumination, the temperature of the cocrystal sharply increases in a short time with high PT conversion efficiency (η=18.8 %), which is due to the active non-radiative pathways and inhibition of radiative transition process, as revealed by femtosecond transient absorption spectroscopy. This is the first PT conversion cocrystal, which not only provides insights for the development of novel PT materials, but also paves the way of designing functional materials with appealing applications.

Cocrystals Strategy towards Materials for Near‐Infrared Photothermal Conversion and Imaging

Cocrystal engineering with a noncovalent assembly feature by simple constituent units has inspired great interest and has emerged as an efficient and versatile route to construct functional materials, especially for the fabrication of novel and multifunctional materials, due to the collaborative strategy in the distinct constituent units. Meanwhile, the precise crystal architectures of organic cocrystals, with long-range order as well as free defects, offer the opportunity to unveil the structure-property and charge-transfer-property relationships, which are beneficial to provide some general rules in rational design and choice of functional materials. In this regard, an overview of organic cocrystals in terms of assembly, containing the intermolecular interactions and growth methods, two functionality-related factors including packing structure and charge-transfer nature, and those advanced and novel functionalities, is presented. An outlook of future research directions and challenges for organic cocrystal is also provided.

Xiaotao Zhang

Papers

Organic Semiconductor Single Crystals for Electronics and Photonics.

Organic crystalline materials in flexible electronics

2D Organic Materials for Optoelectronic Applications

Cocrystals Strategy towards Materials for Near‐Infrared Photothermal Conversion and Imaging

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials