One of the most charming and challenging topics in organic chemistry is the selective C-H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C-H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C-H bond activation on Au(111) surfaces and monoselective ortho C-H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C-H bond activation.
The formation of additional phenyl rings on surfaces is of particular interest because it allows for the building-up of surface covalent organic frameworks. In this work, we show for the first time that the cyclotrimerization of acetyls to aromatics provides a promising approach to 2D conjugated covalent networks on surfaces under ultrahigh vacuum. With the aid of scanning tunneling microscopy, we have systematically studied the reaction pathways and the products. With the combination of density functional theory calculations and X-ray photoemission spectroscopy, the surface-assisted reaction mechanism, which is different from that in solution, was explored.
Simultaneous improvement of electromagnetic interference shielding and mechanical properties of a multilayer-structured CNT/regenerated cellulose composite.
Hierarchical control of chemical reactions is being considered as one of the most ambitious and challenging topics in modern organic chemistry. In this study, we have realized the one-by-one scission of the X-H bonds (X = N and C) of aromatic amines in a controlled fashion on the Cu(111) surface. Each dehydrogenation reaction leads to certain metal-organic supramolecular structures, which were monitored in single-bond resolution via scanning tunneling microscopy and noncontact atomic force microscopy. Moreover, the reaction pathways were elucidated from X-ray photoelectron spectroscopy measurements and density functional theory calculations. Our insights pave the way for connecting molecules into complex structures in a more reliable and predictable manner, utilizing carefully tuned stepwise on-surface synthesis protocols.
Lightweight
conductive polymer composites based on biomass could
be a promising candidate for electromagnetic interference (EMI) shielding
application. Herein, tailoring porous microstructure and regulating
the distribution of carbon nanotubes (CNTs) in cellulose composites
are attempts to achieve highly efficient EMI shielding properties
accompanying desired mechanical property and low density. Specifically,
aligned porous structure is fabricated by ice-template freeze-drying
method; meanwhile, CNT is regulated to decorate inside the cellulose
matrix (CNT-matrix/cellulose porous composites) or to directly bind
over the cellulose cell walls (CNT-interface/cellulose porous composites).
It is found that, owing to the preferential distribution of CNT on
the cell walls, the CNT-interface/cellulose porous composites possess
a very high electrical conductivity of 38.9 S m–1 with an extremely low percolation threshold of 0.0083 vol % with
regard to CNT-matrix/cellulose porous composites. Therefore, a shielding
effectiveness of 40 dB with merely 0.51 vol % CNT under a thickness
of 2.5 mm is achieved in CNT-interface/cellulose porous composites,
which is attributed to efficient multiple reflections and the accompanying
absorption with promoted conductivity and better-defined porous structure.
More laudably, the CNT-interface/cellulose porous composites reveal
a superior mechanical property with a specific modulus of 279 MPa
g–1 cm3. The value behind the current
work is to pave an effective way to fabricate environmentally benign,
high-performance EMI shielding materials to practically boost numerous
advanced applications of cellulose.
Ten 3 beta-ecgonine analogues were synthesized and characterized by 1H and 13C NMR, MS, and elemental analysis. The compounds were synthesized as (-)-stereoisomers from (-)-cocaine. These compounds were assessed for their ability to inhibit [3H]cocaine binding to rat striatal tissue and to inhibit [3H]DA uptake into rat striatal synaptosomes. In this series of compounds, the length of the spacer between the aryl group and the tropane skeleton ranged from 1 to 4 bond distances, and conformational flexibility of the linkage and orientation of the aryl ring system were controlled by various types of linkages. The most potent of the analogues was methyl-(1R-2-exo-3-exo)-8-methyl-3-(beta-styrenyl)-8-azabicyclo[3. 2.1] octane-2-carboxylate. One of the less potent compounds was found to inhibit [3H]cocaine binding and [3H]DA uptake with significantly different IC50 values, in contrast to 14 other 3 beta-substituted analogues. Molecular modeling and CoMFA analysis were used to obtain a rigorous structure-function relationship for the studied compounds. The results showed that the potencies of these 3 beta-substituted ecgonine methyl esters were dominated by steric effects and were acutely sensitive to the distance between the aryl ring and the tropane skeleton and to the orientation of the aryl ring system relative to the tropane skeleton. The current study provides a clearer picture of the shape and size of the putative hydrophobic binding pocket for the 3 beta substituent at the cocaine receptor as well as emphasizing the importance of a drug's free energy of solvation in obtaining structure-activity relationships.
Controlling
the regioselectivity of C–H activation in unimolecular
reactions is of great significance for the rational synthesis of functional
graphene nanostructures, which are called nanographenes. Here, we
demonstrate that the adsorption of tetranaphthyl-
p
-terphenyl precursors on metal surfaces can completely change the
cyclodehydrogenation route and lead to obtaining planar benzo-fused
perihexacenes rather than double [7]helicenes during solution synthesis.
The course of the on-surface planarization reactions is monitored
using scanning probe microscopy, which unambiguously reveals the formation
of dibenzoperihexacenes and the structures of reaction intermediates.
The regioselective planarization can be attributed to the flattened
adsorption geometries and the reduced flexibility of the precursors
on the surfaces, in addition to the different mechanism of the on-surface
cyclodehydrogenation from that of the solution counterpart. We have
further achieved the on-surface synthesis of dibenzoperioctacene by
employing a tetra-anthryl-
p
-terphenyl precursor.
The energy gaps of the new nanographenes are measured to be approximately
2.1 eV (dibenzoperihexacene) and 1.3 eV (dibenzoperioctacene) on a
Au(111) surface. Our findings shed new light on the regioselectivity
in cyclodehydrogenation reactions, which will be important for exploring
the synthesis of unprecedented nanographenes.
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