Prussian blue analogue derived from leather waste as a bifunctional catalyst in zinc-air batteries.

A Prussian blue analogue was synthesized using biomass leather waste as a precursor by doping with Co2+ ions. This material, demonstrates good performance in both the oxygen reduction reaction and oxygen evolution reaction, and exhibits excellent charge-discharge performance and stability in zinc-air batteries.

Two side chains, three supramolecules: exploration of fluorenone derivatives towards crystal engineering.

Structural diversity obtained through two-dimensional molecular self-assembly induced by the chain length effect has gained immense attention, not only because of its significance in crystal engineering but also for its potential application in nanoscience and nanotechnology. Three kinds of fluorenone derivative, named F-C7C7, F-C14C7, and F-C14C14, were synthesized and used for systematic exploration of their crystalline difference. At first, scanning electron microscopy and X-ray powder diffraction were performed to investigate their differences in morphology and three-dimensional crystal structure. Then scanning tunneling microscopy experiments were conducted to compare the self-assembled monolayers. Moreover, different solvents were used to repeatedly investigate the occurrence of structural diversity. F-C7C7 could not self-assemble into a stable monolayer on the graphite surface under ambient conditions due to its weak molecule-substrate interaction. F-C14C7 was observed to self-assemble into twist, plier-like, octamer-curve, and random structures in 1-octanoic acid, 1-phenyloctane, n-tetradecane, and dichloromethane, respectively. However, when the same solvents were used and at similar concentrations, the F-C14C14 molecules were arranged into interval, mixed, linear, and plier-like configurations. These self-assembled nanopatterns formed under the driving forces of dipole-dipole interactions, hydrogen bonds, and chain-chain, molecule-substrate, and molecule-solvent van der Waals interactions. Furthermore, from the viewpoint of thermal analysis, differential scanning calorimetry, as well as polarized optical microscopy, was performed to further elucidate the difference between these three compounds in the solid and liquid crystal states. The present system is believed to provide understanding of how the chain length effect induces different crystalline properties, and to open up the possibility of fabricating diverse self-assembled networks for crystal engineering.

Halogen bonding versus hydrogen bonding induced 2D self-assembled nanostructures at the liquid-solid interface revealed by STM.

We design a bifunctional molecule (5-bromo-2-hexadecyloxy-benzoic acid, 5-BHBA) with a bromine atom and a carboxyl group and its two-dimensional self-assembly is experimentally and theoretically investigated by using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The supramolecular self-organization of 5-BHBA in two different solvents (1-octanoic acid and n-hexadecane) at the liquid-solid interface at different solution concentrations is obviously different due to the cooperative and competitive intermolecular halogen and hydrogen bonds. Three kinds of nanoarchitectures composed of dimers, trimers and tetramers are formed at the 1-octanoic acid/graphite interface based on -COOHHOOC-, triangular C[double bond, length as m-dash]OBrH-C, -BrO(H), BrBr, and OH interactions. Furthermore, by using n-hexadecane as the solvent, two kinds of self-assembled linear patterns can be observed due to the coadsorption, in which the dimers are formed by intermolecular -COOHHOOC- hydrogen bonds. The molecule-solvent and solvent-solvent van der Waals force and intermolecular hydrogen bonds dominate the formation of coadsorbed patterns. We propose that the cooperative and competitive halogen and hydrogen bonds are related to the polarity of the solvent and the type of molecule-solvent interaction. The intermolecular binding energy of different dimers and their stability are supported by theoretical calculations. The result provides a new and innovative insight to induce the 2D self-assembled nanostructures by halogen and hydrogen bonds at the liquid-solid interface.

Cooperation and competition between halogen bonding and van der Waals forces in supramolecular engineering at the aliphatic hydrocarbon/graphite interface: position and number of bromine group effects.

Herein, the photophysical properties of two π-conjugated thienophenanthrene derivatives (6,9- and 5,10-DBTD) are reported. Their self-assembled monolayers in aliphatic hydrocarbon solvents under different concentrations were investigated by scanning tunneling microscopy on a graphite surface. The STM results revealed that the self-assembled structures of the two geometrical isomers exhibited absolutely different behaviors. At the aliphatic solvent/graphite interface, 6,9-DBTD produced almost a single stable coassembled linear structure, except for that with n-tridecane as the solvent. However, the self-assembly of 5,10-DBTD showed structural diversity, and it presented a gradient variety through increasing the chain length of the aliphatic solvents as well as the solution concentration. All ordered self-assembled adlayers critically depend on not only the interchain van der Waals (vdW) interactions, but also on multiple intermolecular interactions, including BrO[double bond, length as m-dash]C and BrS hetero-halogen bonds, homo-BrBr interactions, and HBr and HO hydrogen bonds. We proposed that the cooperation and competition of the intermolecular interactions involving a Br atom and interchain vdW forces induce this structural variety. Density functional theory calculations support to unravel the different elementary structural units based on halogen bonds and hydrogen bonds and were useful tools to dissect and explain the formation mechanism.

Controllable Orientation of Ester-Group-Induced Intermolecular Halogen Bonding in a 2D Self-Assembly.

Halogen bonding with high specificity and directionality in the geometry has proven to be an important type of noncovalent interaction to fabricate and control 2D molecular architectures on surfaces. Herein, we first report how the orientation of the ester substituent for thienophenanthrene derivatives (5,10-DBTD and 5,10-DITD) affects positive charge distribution of halogens by density functional theory, thus determining the formation of an intermolecular halogen bond and different self-assembled patterns by scanning tunneling microscopy. The system presented here mainly includes heterohalogen X···O═C and X···S halogen bonds, H···Br and H···O hydrogen bonds, and I···I interaction, where the directionality and strength of such weak bonds determine the molecular arrangement by varying the halogen substituent. This study provides a detailed understanding of the role of ester orientation, concentration, and solvent effects on the formation of halogen bonds and proves relevant for identification of multiple halogen bonding in supramolecular chemistry.

Fabrication of chiral networks for a tri-substituted anthraquinone derivative using molecular self-assembly.

Chiral structures are recorded, with the adsorption of an achiral anthraquinone derivative and co-adsorption of achiral solvent on an achiral surface. Dimer, trimer and tetramer aggregations are observed while only the tetramer-dimer combination constructs the whole monolayer, and the formation mechanism is explained from the thermodynamic and kinetic viewpoints.

Effects of the position and number of bromine substituents on the concentration-mediated 2D self-assembly of phenanthrene derivatives.

The effects of the position and number of bromine substituents on the self-assembled patterns of phenanthrene derivatives by changing multiple weak intermolecular interactions were investigated at the 1-octanoic acid/graphite interface at different concentrations by scanning tunneling microscopy. Two Br substituted DBHP molecules (2,7-DBHP, 3,6-DBHP) and BHP without a Br group formed a linear lamellar pattern by the van der Waals interactions between the alkoxyl chains in each lamella at high concentrations, which forces the phenanthrene derivatives to self-organize in a π-π stacked edge-on conformation. On decreasing the solution concentration, owing to the molecule-molecule van der Waals force and BrBr halogen bonds or the molecule-solvent cooperative BrO (C[double bond, length as m-dash]O) hydrogen and BrHO-hydrogen bonds, 2,7-DBHP molecules were found to form two kinds of network structures, whereas 3,6-DBHP molecules formed only a zigzag pattern due to the intermolecular BrBr van der Waals type interactions. One bromine substituted phenanthrene derivative (3-DBHP) formed a dislocated linear pattern by two C-HBr hydrogen bonds in each dimer. These observations revealed that an important modification of the position and number of halogen substituents might dramatically change the self-assembly behaviors by different intermolecular interactions including BrBr and BrO halogen bonding, BrBr van der Waals type interactions, and HBr hydrogen bonding. DFT calculations were explored to unravel how slightly tuning the molecular structure defines the geometry of a 2D self-assembled nanoarchitecture through the different elementary structural units having BrBr and BrH interactions.

STM investigation of structural isomers: alkyl chain position induced self-assembly at the liquid/solid interface.

Investigating and regulating the self-assembly structure is of great importance in 2D crystal engineering and it is also gaining significant interest in surface studies. In this work, we systematically explored the variation of self-assembled patterns induced by the changeable side chain position. Moreover, molecules with different alkyl chain lengths (n = 15, 16) were also synthesized and probed for the purpose of understanding how an odd/even number of carbon atoms in the peripheral chains can affect the molecular adlayers. Structural isomers of bis-substituted anthraquinone derivatives 1,8-A-2OCn, 2,6-A-2OCn, 1,4-A-2OCn and 1,5-A-2OCn (n = 15, 16) were used and investigated by STM. 1,8-A-2OC16 and 1,8-A-2OC15 molecules adopted Z-like I and Linear I structures, respectively. 2,6-A-2OC16 and 2,6-A-2OC15 molecules were severally arranged in Linear II and Linear III configurations. 1,4-A-2OCn (n = 15, 16) molecules were staggered in a Z-like II fashion and 1,5-A-2OCn (n = 15, 16) molecules displayed a Linear IV nanostructure. Therefore, we arrive at a conclusion that self-assembly structures of anthraquinone isomers are chain-position-dependent, and designing isomeric compounds can be taken into consideration in regulating assembled structures. Besides, 2D nanopatterns of 1,8-A-2OCn and 2,6-A-2OCn can be regulated by the odd/even property of the side chains, but this is not the case for 1,4-A-2OCn and 1,5-A-2OCn, ascribed to the difference in driving forces for them. It is believed that the results are of significance to the alkyl chain position induced assembly configurations and surface research studies of structural isomers.

Concentration dependent halogen-bond density in the 2D self-assembly of a thienophenanthrene derivative at the aliphatic acid/graphite interface.

The supramolecular patterns of a thienophenanthrene derivative could be switched among dissimilar polymorphs with different halogen-bond densities by solution concentration, which is demonstrated through a combination of STM and density functional theory (DFT) calculations.

Hydrogen-bonding-induced polymorphous phase transitions in 2D organic nanostructures.

The 2D self-assembly of various 2-hydroxy-7-alkoxy-9-fluorenone (HAF) molecules has been investigated by scanning tunneling microscopy (STM) at the liquid/solid interface. A systematic study revealed that HAF molecules with different numbers of carbon atoms in their alkoxy chains could form two or three different kinds of nanostructures, that is, less-ordered, flower-like, and zig-zag patterns, owing to the formation of different types of intermolecular hydrogen bonds. The observed structural transition was found to be driven by molecular thermodynamics, surface diffusion, and the voltage pulse that was applied to the STM tip. The zig-zag pattern was the most stable of these configurations. An odd-even effect on the flower-like structure, as induced by the odd and even number of carbon atoms in the side chain, was observed by STM. The influence of the odd-even effect on the melting point has a close relationship with the molecular self-assembled pattern. Our results are significant for understanding the influence of hydrogen-bonding interactions on the dominant adsorption behavior on the surface and provide a new visual approach for observing the influence of the odd-even effect on the phase transition.