State Key Laboratory of Supramolecular Structure and Materials

The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

Shine on you crazy dots: A rapid and high-output strategy allows the fabrication of polymer-like carbon dots (CDs) with quantum yields as high as ca. 80 %. This value is the highest reported to date for fluorescent carbon-based materials, and gives promise for their application in multicolor-patterning and biosensors. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

At present, the actual mechanism of the photoluminescence (PL) of fluorescent carbon dots (CDs) is still an open debate among researchers. Because of the variety of CDs, it is highly important to summarize the PL mechanism for these kinds of carbon materials; doing so can guide the development of effective synthesis routes and novel applications. This review will focus on the PL mechanism of CDs. Three types of fluorescent CDs were involved: graphene quantum dots (GQDs), carbon nanodots (CNDs), and polymer dots (PDs). Four reasonable PL mechanisms have been confirmed: the quantum confinement effect or conjugated π-domains, which are determined by the carbon core; the surface state, which is determined by hybridization of the carbon backbone and the connected chemical groups; the molecule state, which is determined solely by the fluorescent molecules connected on the surface or interior of the CDs; and the crosslink-enhanced emission (CEE) effect. To give a thorough summary, the category and synthesis routes, as well as the chemical/physical properties for the CDs, are briefly introduced in advance.

Carbon dots (CDs), as a new type of carbon-based nanomaterial, have attracted broad research interest for years, because of their diverse physicochemical properties and favorable attributes like good biocompatibility, unique optical properties, low cost, ecofriendliness, abundant functional groups (e.g., amino, hydroxyl, carboxyl), high stability, and electron mobility. In this Outlook, we comprehensively summarize the classification of CDs based on the analysis of their formation mechanism, micro-/nanostructure and property features, and describe their synthetic methods and optical properties including strong absorption, photoluminescence, and phosphorescence. Furthermore, the recent significant advances in diverse applications, including optical (sensor, anticounterfeiting), energy (light-emitting diodes, catalysis, photovoltaics, supercapacitors), and promising biomedicine, are systematically highlighted. Finally, we envisage the key issues to be challenged, future research directions, and perspectives to show a full picture of CDs-based materials.

Strongly fluorescent graphene quantum dots (GQDs) have been prepared by one-step solvothermal method with PL quantum yield as high as 11.4%. The GQDs have high stability and can be dissolved in most polar solvents. Because of fine biocompatibility and low toxicity, GQDs are demonstrated to be excellent bioimaging agents.

Abstract Despite the various synthesis methods to obtain carbon dots (CDs), the bottom‐up methods are still the most widely administrated route to afford large‐scale and low‐cost synthesis. However, as CDs are developed with increasing reports involved in producing many CDs, the structure and property features have changed enormously compared with the first generation of CDs, raising classification concerns. To this end, a new classification of CDs, named carbonized polymer dots (CPDs), is summarized according to the analysis of structure and property features. Here, CPDs are revealed as an emerging class of CDs with distinctive polymer/carbon hybrid structures and properties. Furthermore, deep insights into the effects of synthesis on the structure/property features of CDs are provided. Herein, the synthesis methods of CDs are also summarized in detail, and the effects of synthesis conditions of the bottom‐up methods in terms of the structures and properties of CPDs are discussed and analyzed comprehensively. Insights into formation process and nucleation mechanism of CPDs are also offered. Finally, a perspective of the future development of CDs is proposed with critical insights into facilitating their potential in various application fields.

The high pressure structures, metallization, and superconductivity of recently synthesized H2-containing compounds (H2S)2H2 are elucidated by ab initio calculations. The ordered crystal structure with P1 symmetry is determined, supported by the good agreement between theoretical and experimental X-ray diffraction data, equation of states, and Raman spectra. The Cccm structure is favorable with partial hydrogen bond symmetrization above 37 GPa. Upon further compression, H2 molecules disappear and two intriguing metallic structures with R3m and Im-3m symmetries are reconstructive above 111 and 180 GPa, respectively. The predicted metallization pressure is 111 GPa, which is approximately one-third of the currently suggested metallization pressure of bulk molecular hydrogen. Application of the Allen-Dynes-modified McMillan equation for the Im-3m structure yields high Tc values of 191 K to 204 K at 200 GPa, which is among the highest values reported for H2-rich van der Waals compounds and MH3 type hydride thus far.

Abstract The bandgap in graphene‐based materials can be tuned from 0 eV to that of benzene by changing size and/or surface chemistry, making it a rising carbon‐based fluorescent material. Here, the surface chemistry of small size graphene (graphene quantum dots, GQDs) is tuned programmably through modification or reduction and green luminescent GQDs are changed to blue luminescent GQDs. Several tools are employed to characterize the composition and morphology of resultants. More importantly, using this system, the luminescence mechanism (the competition between both the defect state emission and intrinsic state emission) is explored in detail. Experiments demonstrate that the chemical structure changes during modification or reduction suppresses non‐radiative recombination of localized electron‐hole pairs and/or enhances the integrity of surface π electron network. Therefore the intrinsic state emission plays a leading role, as opposed to defect state emission in GQDs. The results of time‐resolved measurements are consistent with the suggested PL mechanism. Up‐conversion PL of GQDs is successfully applied in near‐IR excitation for bioimaging.

Two types of carbon dots (C dots) exhibiting respective excitation-independent blue emission and excitation-dependent full-color emissions have been synthesized via a mild one-pot process from chloroform and diethylamine. This new bottom-up synthetic strategy leads to highly stable crystalline C dots with tunable surface functionalities in high reproducibility. By detailed characterization and comparison of the two types of C dots, it is proved concretely that the surface functional groups, such as C═O and C═N, can efficiently introduce new energy levels for electron transitions and result in the continuously adjustable full-color emissions. A simplified energy level and electron transition diagram has been proposed to help understand how surface functional groups affect the emission properties. By taking advantage of the unique excitation-dependent full-color emissions, various new applications can be anticipated. Here, as an example, a ratiometric pH sensor using two emission wavelengths of the C dots as independent references has been constructed to improve the reliability and accuracy, and the pH sensor is applied to the measurement of intracellular pH values and cancer diagnosis.

A chameleon under pressure: The observed piezochromic behavior of the title compound (BP2VA) was found to depend on its molecular aggregation state and specifically on the strength of the π–π interaction between the anthracene rings of adjacent molecules. When BP2VA is ground or placed under pressure, its molecular aggregation state changes, and a red shift in the fluorescence emission from green via orange to red occurs (see picture). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Farbenspiele: Polymerartige Kohlenstoffpunkte (CDs) können schnell und in großen Mengen hergestellt werden. Mit ca. 80 % erzielen die CDs die bisher höchsten Quantenausbeuten für fluoreszierende Kohlenstoffmaterialien, woraus sich Anwendungsmöglichkeiten in Vielfarben-Musterbildung und Biosensoren ergeben könnten. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Near-infrared-emissive polymer-carbon nanodots (PCNDs) are fabricated by a newly developed facile, high-output strategy. The PCNDs emit at a wavelength of 710 nm with a quantum yield of 26.28%, which is promising for deep biological imaging and luminescent devices. Moreover, the PCNDs possess two-photon fluorescence; in vivo bioimaging and red-light-emitting diodes based on these PCNDs are demonstrated. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Abstract In an organic electroluminescent (EL) device, the recombination of injected holes and electrons produces what appears to be an ion‐pair or charge‐transfer (CT) exciton, and this CT exciton decays to produce one photon directly, or relaxes to a low‐lying local exciton (LE). Thus the full utilization of both the energy of the CT exciton and the LE should be a pathway for obtaining high‐efficiency EL. Here, a twisting donor‐acceptor (D‐A) triphenylamine‐imidazol molecule, TPA‐PPI, is reported: its synthesis, photophysics, and EL performance. Prepared by a manageable, one‐pot cyclizing reaction, TPA‐PPI exhibits deep‐blue emission with high quantum yields (90%) both in solution and in the solid state. Fluorescent solvatochromic experiments for TPA‐PPI solutions show a red‐shift of 57 nm (3032 cm −1 ) from low‐polarity hexane (406 nm) to high‐polarity acetonitrile (463 nm), accompanied by the gradual disappearance of the vibrational band in the spectra with increased solvent polarity. The photophysical investigation and DFT analysis suggest an intercrossed CT and LE excited state of the TPA‐PPI, originating from its twisting D‐A configuration. This is a rare instance that a CT‐state material shows highly efficient deep‐blue emission. EL characterization demonstrates that, as a deep‐blue emitter with CIE coordinates of (0.15, 0.11), the performance of a TPA‐PPI‐based device is rather excellent, displaying a maximum current efficiency of >5.0 cd A −1 , and a maximum external quantum efficiency of >5.0%, corresponding to a maximum internal quantum efficiency of >25%. The effective utilization of the excitation energy arising from materials with intercrossed‐excited‐state (LE and CT) characters is thought to be beneficial for the improved efficiency of EL devices.

We clarified the chemical structure of typical “bottom-up” CDs and proved that IPCA is the molecular state photoluminescence center.

With the rapid development of optoelectronic fields, electrochromic (EC) materials and devices have received remarkable attention and have shown attractive potential for use in emerging wearable and portable electronics, electronic papers/billboards, see-through displays, and other new-generation displays, due to the advantages of low power consumption, easy viewing, flexibility, stretchability, etc. Despite continuous progress in related fields, determining how to make electrochromics truly meet the requirements of mature displays (e.g., ideal overall performance) has been a long-term problem. Therefore, the commercialization of relevant high-quality products is still in its infancy. In this review, we will focus on the progress in emerging EC materials and devices for potential displays, including two mainstream EC display prototypes (segmented displays and pixel displays) and their commercial applications. Among these topics, the related materials/devices, EC performance, construction approaches, and processing techniques are comprehensively disscussed and reviewed. We also outline the current barriers with possible solutions and discuss the future of this field.

In principle, the ratio (Φ) of the maximum quantum efficiencies for electroluminescence (EL) to photoluminescence (PL) can be expected to approach unity, if the exciton (bound electron–hole pair) generated from the recombination of injected electrons and holes in OLEDs has a sufficiently weak binding energy. However, seldom are examples of Φ > 25% reported in OLEDs because of the strongly bound excitons for most organic semiconductors in nature. Here, a twisting donor–acceptor triphenylamine‐thiadiazol molecule (TPA‐NZP) exhibits fluorescent emission through a hybridized local and charge‐transfer excited state (HLCT), which is demonstrated from both fluorescent solvatochromic experiment and quantum chemical calculations. The HLCT state possesses two combined and compatible characteristics: a large transition moment from a local excited (LE) state and a weakly bound exciton from a charge transfer (CT) state. The former contributes to a high‐efficiency radiation of fluorescence, while the latter is responsible for the generation of a high fraction of singlet excitons. Using TPA‐NZP as the light‐emitting layer in an OLED, high Φ values of 93% (at low brightness) and 50% (at high brightness) are achieved, reflecting sufficient employment of the excitons in the OLED. Characterization of the EL device shows a saturated deep‐red emission with CIE coordinates of (0.67, 0.32), accompanied by a rather excellent performance with a maximum luminance of 4574 cd m −2 and a maximum external quantum efficiency (η ext ) of ∼2.8%. The HLCT state is a new way to realize high‐efficiency of EL devices.

The development of near-infrared (NIR) organic light-emitting diodes (OLEDs) is of growing interest. Donor-acceptor (D-A) chromophores have served as an important class of NIR materials for NIR OLED applications. However, the external quantum efficiencies (EQEs) of NIR OLEDs based on conventional D-A chromophores are typically below 1 %. Reported herein is a butterfly-shaped D-A compound, PTZ-BZP. A PTZ-BZP film displayed strong NIR fluorescence with an emission peak at 700 nm, and the corresponding quantum efficiency reached 16 %. Remarkably, the EQE of the NIR OLED based on PTZ-BZP was 1.54 %, and a low efficiency roll-off was observed, as well as a high radiative exciton ratio of 48 %, which breaks through the limit of 25 % in conventional fluorescent OLEDs. Experimental and theoretical investigations were carried out to understand the excited-state properties of PTZ-BZP.

Using commercially activated carbon, we developed a simple and effective direct chemical oxidation route to prepare good biocompatible multicolor photoluminescent carbon dots.

Tissue engineering is a promising and revolutionary strategy to treat patients who suffer the loss or failure of an organ or tissue, with the aim to restore the dysfunctional tissues and enhance life expectancy. Supramolecular adhesive hydrogels are emerging as appealing materials for tissue engineering applications owing to their favorable attributes such as tailorable structure, inherent flexibility, excellent biocompatibility, near-physiological environment, dynamic mechanical strength, and particularly attractive self-adhesiveness. In this review, the key design principles and various supramolecular strategies to construct adhesive hydrogels are comprehensively summarized. Thereafter, the recent research progress regarding their tissue engineering applications, including primarily dermal tissue repair, muscle tissue repair, bone tissue repair, neural tissue repair, vascular tissue repair, oral tissue repair, corneal tissue repair, cardiac tissue repair, fetal membrane repair, hepatic tissue repair, and gastric tissue repair, is systematically highlighted. Finally, the scientific challenges and the remaining opportunities are underlined to show a full picture of the supramolecular adhesive hydrogels. This review is expected to offer comparative views and critical insights to inspire more advanced studies on supramolecular adhesive hydrogels and pave the way for different fields even beyond tissue engineering applications.

Self-assembly of colloidal microspheres or nanospheres is an effective strategy for fabrication of ordered nanostructures. By combination of colloidal self-assembly with nanofabrication techniques, two-dimensional (2D) colloidal crystals have been employed as masks or templates for evaporation, deposition, etching, and imprinting, etc. These methods are defined as "colloidal lithography", which is now recognized as a facile, inexpensive, and repeatable nanofabrication technique. This paper presents an overview of 2D colloidal crystals and nanostructure arrays fabricated by colloidal lithography. First, different methods for fabricating self-assembled 2D colloidal crystals and complex 2D colloidal crystal structures are summarized. After that, according to the nanofabrication strategy employed in colloidal lithography, related works are reviewed as colloidal-crystal-assisted evaporation, deposition, etching, imprinting, and dewetting, respectively.