Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. Here, we report on the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from two of the rotors are found to originate, not from the localized excited state as one might expect, but from unanticipated through-space aromatic-dimer states. We demonstrate that these relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission. Computational modeling also suggests that the formation of aromatic-dimer excited states may account for the photophysical properties of a previously reported luminogen. These results imply, therefore, that this is a general phenomenon that should be taken into account when designing and interpreting the fluorescent outputs of luminescent probes and optoelectronic devices based on fluorescent molecular rotors.

Succeeding graphene, monoelemental two-dimensional (2D) materials such as germanene and silicene, coined as "Xenes", have attracted vast scientific and technological interests. Adding covalently bonded hydrogen on both sides of germanene leads to germanane (i.e., hydrogen-terminated germanene, GeH). Further, the covalent functionalization of germanane allows the tuning of its physical and chemical properties. Diverse variants of germananes have been synthesized, but current research is primarily focused on their fundamental properties. As a case in point, their applications as photo-and electrocatalysts in the field of modern energy conversion have not been explored. Here, we prepare 2D germanene-based materials, specifically germanane and germananes functionalized by various alkyl chains with different terminal groupsgermanane with methyl, propyl, hydroxypropyl, and 2-(methoxycarbonyl)ethyland investigate their structural, morphological, optical, electronic, and electrochemical properties. The bond geometries of the functionalized structures, their formation energies, and band gap values are investigated by density functional theory calculations. The functionalized germananes are tested as photoelectrocatalysts in the hydrogen evolution reaction (HER) and photo-oxidation of water. The performance of the germananes is influenced by the functionalized groups, where the germanane with −CH 2 CH 2 CH 2 OH termination records the lowest HER overpotentials and with −H termination reaches the highest photocurrent densities for water oxidation over the entire visible spectral region. These positive findings serve as an overview of organic functionalization of 2D germananes that can be expanded to other "Xanes" for targeted tuning of the optical and electronic properties for photo-and electrochemical energy conversion applications.

The chemistry of graphene and its derivatives is one of the hottest topics of current material science research. The derivatisation of graphene is based on various approaches, and to date functionalization with halogens, hydrogen, various functional groups containing oxygen, sulfur, nitrogen, phosphorus, boron, and several other elements have been reported. Most of these functionalizations are based on sp hybridization of carbon atoms in the graphene skeleton, which means the formation of out-of-plane covalent bonds. Several elements were also reported for substitutional modification of graphene, where the carbon atoms are substituted with atoms like nitrogen, boron, and several others. From tens of functional groups, for only two of them were reported full functionalization of graphene skeleton and formation of its stoichiometric counterparts, fluorographene and hydrogenated graphene. The functionalization of graphene is crucial for most of its applications including energy storage and conversion devices, electronic and optic applications, composites, and many others.

Two-dimensional materials attract enormous attention across several scientific fields. The current demands in nano- and optoelectronics, semiconductors, or in catalysis have been accelerating the research process in the field of 2D materials. Among the 14th group 2D materials besides graphene and silicene, layered germanium represents a promising candidate for another class of materials, and its functionalization represents a way to tune either its electronic or optical properties. Here, the exfoliation and functionalization of germanane surface is achieved via abstraction of hydrogen from Ge–H bond and its subsequent alkylation utilizing n-alkyl halides or trifluoromethyl (CF3) group containing benzyl halides. Composition of materials is confirmed by several methods including FT-IR, Raman, X-ray photoelectron, and energy-dispersive X-ray spectroscopy as well as X-ray powder diffraction. Scanning and transmission electron spectroscopy is used to reveal the layered morphology of functionalized germananes.

A series of monosubstituted pyrimidinium and pyrazinium triflates and 3,5-disubstituted pyridinium triflates were prepared and tested as simple catalysts of oxidations with hydrogen peroxide, using sulfoxidation as a model reaction. Their catalytic efficiency strongly depends on the type of substituent and is remarkable for derivatives with an electron-withdrawing group, showing reactivity comparable to that of flavinium salts which are the prominent organocatalysts for oxygenations. Because of their high stability and good accessibility, 4-(trifluoromethyl)pyrimidinium and 3,5-dinitropyridinium triflates are the catalysts of choice and were shown to catalyze oxidation of aliphatic and aromatic sulfides to sulfoxides, giving quantitative conversions, high preparative yields and excellent chemoselectivity. The high efficiency of electron-poor heteroarenium salts is rationalized by their ability to readily form adducts with nucleophiles, as documented by low pKR+ values (pKR+ < 5) and less negative reduction potentials (Ered > -0.5 V). Hydrogen peroxide adducts formed in situ during catalytic oxidation act as substrate oxidizing agents. The Gibbs free energies of oxygen transfer from these heterocyclic hydroperoxides to thioanisole, obtained by calculations at the B3LYP/6-311++g(d,p) level, showed that they are much stronger oxidizing agents than alkyl hydroperoxides and in some cases are almost comparable to derivatives of flavin hydroperoxide acting as oxidizing agents in monooxygenases.

(1 of 11)2D monoelemental group 14 materials beyond graphene, such as silicene and germanene, have recently gained a lot of attention. Covalent functionalization of group 14 layered materials can lead to significant tuning of their properties. While optical and electronic properties of germanene, silicene, and their derivatives have been studied in detail previously, there is no information on their electrochemistry and toxicity. Herein, electrochemical applications of 2D siloxene, germanane, and methylgermanane, specifically for detection of an important biomarker, dopamine, as well as catalyzation of oxygen reduction and hydrogen evolution reactions, which are important in energy applications, are explored. Among the three materials, germanane portrays most superior properties for the electrochemical applications mentioned. All three materials possess fast heterogeneous electron transfer rates, relative to bare glassy carbon electrodes. In addition, toxicity studies of these materials are conducted to gain insights on their possible harmful effects toward human health. The results of this study show siloxene nontoxic while germanane and methylgermanane impose dose-dependent toxicity. Interestingly, methylation successfully reduce the toxicity of methylgermanane at lower concentrations. These studies provide fundamental insights into electrochemical and toxic properties of functionalized group 14 layered materials for future electrochemical applications.

For the past decade, researchers have been trying to understand the mechanism of the thermal reduction of graphite oxide. Because deuterium is widely used as a marker in various organic reactions, we wondered if deuterium-labeled graphite oxide could be the key to fully understand this mechanism. Graphite oxides were prepared by the Hofmann, Hummers, Staudenmaier, and Brodie methods, and a deuterium-labeled analogue was synthesized by the Hofmann method. All graphite oxides were analyzed not only using the traditional techniques but also by gas chromatography-mass spectrometry (GC-MS) during exfoliation in hydrogen and nitrogen atmospheres. GC-MS enabled us to compare differences between the chemical compositions of the organic exfoliation products formed during the thermal reduction of these graphite oxides. Nuclear analytical methods (Rutherford backscattering spectroscopy, elastic recoil detection analysis) were used to calculate the concentrations of light elements, including the ratio of hydrogen to deuterium. Combining all of these results we were able to determine graphite oxide's thermal reduction mechanism. Carbon dioxide, carbon monoxide, and water are formed from the thermal reduction of graphite oxide. This process is also accompanied by various radical reactions that lead to the formation of a large amount of carcinogenic volatile organic compounds, and this will have major safety implications for the mass production of graphene.

Materials with few layers have been subjected to extensive research for the last few decades owing to their remarkable properties as for example catalysts, optical and electrical devices, or sensors. The properties and electronic structure of these materials can be tailored by the introduction of substituents. In the case of more reactive species, the modification also can improve stability, which is also an important factor with respect to device fabrication. This review focuses on monoelemental layered materials of Group 15 elements (pnictogens) and in particular their modification, leading to better ambient stability and/or different properties by covalent and non‐covalent modifications. The future modification and application of pnictogens are outlined.