The water heptamer, (H2O)7, is significant in the context of so-called amorphous precursor to the "crystal-like" cubic structures. The neutral (H2O)7 ice-like cluster is a key species in understanding the hydrogen-bonding network transitions between liquid water and ice.
　　Recently, a research team led by Prof. JIANG Ling and Prof. YANG Xueming from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences, in collaboration with Prof. LI Jun from Tsinghua University, has revealed the structural complexity of ice-like clusters.
　　The study was published in Cell Reports Physical Science on February 1.
　　Prof. JIANG's and Prof. YANG's group developed a method of infrared spectroscopy of neutral clusters based on a tunable vacuum ultraviolet free electron laser (VUV-FEL). This method provides a new opportunity for the study of vibrational spectra of a wide variety of neutral clusters that could not be studied before.
　　They measured infrared(IR) spectra of size-selected neutral (H2O)7 using the VUV-FEL-based IR scheme. A variety of diverse bands observed in the IR spectrum of the water heptamer provide evidence for the presence of various low-lying structures at finite temperatures.
　　Prof. LI's team carried out quantum chemical studies to identify the structure of the low-lying isomers and to assign the observed IR spectral features.
　　The consistency of the experimental and calculated infrared spectra establishes general trends in the structural motifs. They found that the major contribution for the experimental spectrum originates from the prism-like isomers, although the minor contribution of the higher-energy cage-like isomers was non-negligible.
　　This study improved the understanding of structural diversity and complexity of water heptamer in the context of the formation and growth of ordered structures in larger systems. (Text by LI Gang and WANG Chong)

A research team led by Prof. CHEN Qing'an from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has realized Nozaki-Hiyama-Kishi (NHK) reaction of alkenes and arylhalides under Ni/Cr cocatalysis.Their findings were published in ACS Catalysis on Jan. 31.Nozaki-Hiyama-Kishi (NHK) reaction is important in synthetic chemistry, which features Ni/Cr-catalyzed coupling between aldehydes and arylhalides.However, compared with conventional aldehydes, alkenes cannot form thermodynamically favored metal-oxygen bonds, thus their NHK reactions have not been achieved yet.In this study, the researchers realized NHK reaction of 1,3-dienes and arylhalides with the assistance of redox active bis(imino)pyridine (PDI) ligand, through which diarylated products can be obtained with high regio- and stereoselectivities. "The key to success relies on the involvement of radical process. CrCl2 serves as a single-electron reductant for the formation of Ni(I) species and aryl radical," said Prof. CHEN.Besides, the resulting diarylated products can be easily transformed into valuable polyaryl thiophene and naphthalene that are interesting building blocks for the manufacture of advanced functional materials."This work is an important complement to NHK reaction. It also provides a paradigm for exploring new functionalization of dienes," said Prof. CHEN.The research was supported by Dalian Outstanding Young Scientific Talent and the National Natural Science Foundation of China.

　　Higher oxygenates, typically referred to alcohols, aldehydes and ketones, are widely used valuable chemicals.
　　Compared with traditional routes, the direct synthesis of higher oxygenates from syngas is a facile and eco-friendly process. However, the low oxygenate yield and active hydrogenation of aldehyde and ketone in this process restrict its industrial applications.
　　Recently, a research team led by Prof. SUN Jian and Prof. GE Qingjie from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has prepared unsaturated oxygenates from syngas and achieved the highly selective production of higher aldehydes and ketones from CO hydrogenation under a mild condition over alkali metal modified iron catalysts.
　　This study was published in Applied Catalysis B: Environmental on Jan. 29.
　　Illustration for the reaction pathway of oxygenates production over Fe-based catalysts (Image by XU Jing)
　　The proposed alkali metal modified iron catalysts, which are synergistic Fe-K series catalysts, could realize the regulation of CO hydrogenation products to C2+ alcohols or C2+ aldehydes and ketones under a mild condition. At a mild temperature of 170°C, the oxygenate selectivity was up to nearly 70 wt%, 88% of which were aldehydes and ketones.
　　The characterizations results showed that the shift of aldehyde-ketone and alcohol was closely related to the electronic and structural effect of K promoter. Proper K promoter could adjust surface chemical environment of catalyst (C-rich and H-lean surface) and reaction intermediates for alcohol to aldehyde shift.
　　The researchers found that the CO non-dissociative sites from Fe2C to Fe by the addition of K could reduce the energy barrier of aldehyde formation, which was favorable for aldehyde production.
　　"This study provides a new idea for the design and application of catalysts to tune the different higher oxygenate distribution in CO hydrogenation," said Prof. SUN.
　　This work was supported by the National Natural Science Foundation of China, the Youth Innovation Promotion Association of CAS, and Liaoning Revitalization Talents Program. (Text by XU Jing)

　　Materials with excitation-dependent emission are promising in applictions in encrypted information storage, multicolor display and anti-counterfeiting fields.
　　Cs2ScCl5·H2O single crystals can show tunable emission colors and its PLQY can be largely enhanced by Sb doping (Image by ZHANG Ruiling)
　　Recently, a research group led by Prof. HAN Keli from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) synthesized an all-inorganic 0D perovskite Cs2ScCl5·H2O with excitation-dependent emission behavior.
　　This study was published in Laser & Photonics Reviews on February 5.
　　The emission color of Cs2ScCl5·H2O could be simply tuned from blue-green to white to yellow by changing excitation wavelengths.
　　The origin of the tunable emission was attributed to the contribution of two different self-trapped exciton (STE) states. 
　　Moreover, the researchers doped Sb3+ ions into Cs2ScCl5·H2O single crystals, leading to enhanced photoluminescence with about 100% photoluminescence quantum yield.
　　"This work provides new insights into the excitation-dependent emission in all-inorganic semiconductors, and presents a strategy to develop environmentally-friendly high-performance emitters," said by Prof. HAN.
　　This study was supported by the National Natural Science Foundation of China. (Text by ZHANG Ruiling)

　　Ferrocenes, a class of important and prevalent metallocenes, have gained much attention owing to their unique structure and excellent performance in material science, medicinal chemistry and catalysis.
　　Therefore, new approaches for the functionalization of ferrocenes are significant in organic chemistry. To date, the direct catalytic C-H (hetero)arylation of ferrocenes is still challenging.
　　Recently, a research group led by Prof. CHEN Qing'an from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) has realized photo-induced catalytic C-H heteroarylation of ferrocenes and ruthenocenes to access pyridyl and pridonyl metallocenes by creating new C-C bonds.
　　Their findings were published in Cell Reports Physical Science on Feb. 16.
　　The researchers found that the protonation of heteroaryl halides probably increased its reduction potential, making it feasible to be reduced by the excited state of photocatalysts.
　　The newly formed C-C bond was constructed through electrophilic radical substitution of the metallocene with a heteroaryl radical, which was generated via an oxidative quenching pathway.
　　"This protocol provides a method with mild and concise conditions to access heteroaryl metallocenes which will be of great significance to material science and catalysis," said Prof. CHEN.
　　The research was supported by Dalian Outstanding Young Scientific Talent and the National Natural Science Foundation of China. (Text by HE Gucheng) 
　　

　　Biomass, the largest renewable carbon resource in the world, offers great potential for sustainable chemical supply.
　　Photocatalysis is recognized as an emerging approach for biomass conversion. Under irradiation, excited photocatalyst can activate biomass substrates into active radical species under mild conditions.
　　Recently, a research team led by Prof. WANG Feng from the Dalian Institute of Chemical Physics (DICP) of the Chinese Academy of Sciences (CAS) systemically discussed recent advanced photocatalytic systems for biomass conversion.
　　This work was published in Nature Reviews Chemistry on Feb. 10.
　　In this study, the researchers summarized advanced photocatalytic systems for value-added chemical production from various raw biomass and derivatives, and discussed the efficient strategies for generating specific radical intermediates from biomass substrate activation and steering their subsequent conversion towards desired products.
　　"We believe that taking full advantage of the unique reactivity of radical intermediates would provide great opportunities to develop more efficient photocatalytic systems for biomass valorization," said Prof. WANG
　　"This work mayprovide a guide for further development of such a promising process," said Prof. WANG. (Text by HUANG Zhipeng)