Solvent-Induced Homochirality in Surface-Confined Low-Density Nanoporous Molecular Networks

Abstract

Induction of chirality in achiral monolayers has garnered considerable attention in the recent past not only due to its importance in chiral resolutions and enantioselective heterogeneous catalysis but also because of its relevance to the origin of homochirality in life. In this contribution, we demonstrate the emergence of macroscopic chirality in multicomponent supramolecular networks formed by achiral molecules at the interface of a chiral solvent and an achiral substrate. The solvent-mediated chiral induction provides a simple, efficient, and versatile approach for the fabrication of homochiral surfaces using achiral building blocks.

Principles of molecular assemblies leading to molecular nanostructures

“…On the other hand, (R)-2-octanol induced a clear bias towards preferential formation of the (−)-type interdigitation pattern and hence the CW honeycomb motif ( figure 2b,d). The solvent-induced homochirality in these monolayers could also be discerned from the preferred orientations of the DBA networks with respect to the normal to the HOPG symmetry axis [23].…”

“…Solvent-induced polymorphism, the effect of co-adsorption as well as the solvent effects on electronic structures have been summarized recently [27]. In addition to their role as dispersing media, chiral enantiopure solvents can influence the handedness of the molecular networks formed at the liquid-solid interface [23,29]. The selfassembly of achiral DBA derivatives at the interface between enantiopure 2-octanol and HOPG resulted in the formation of homochiral monolayers in which the handedness of the porous supramolecular networks was determined by the handedness of the solvent.…”

Effects of Alkyl Chain Length and Hydrogen Bonds on the Cooperative Self‐Assembly of 2‐Thienyl‐Type Diarylethenes at a Liquid/Highly Oriented Pyrolytic Graphite (HOPG) Interface

“…[1][2][3][4][5][6][7][8] Two-dimensionalc rystal engineering at liquid/solid interfaces has attracted growing attention in the last decade. [9][10][11][12][13][14][15] To efficiently design and predict the formationo ft hermodynamically stable molecular ordering formed through self-assembly processes, interplays of various interactions,s uch as molecule-substrate interactions,i ntermoleculari nteraction, [16][17][18][19][20] solvent effects, [21][22][23][24][25] and the balance of enthalpy and entropyt erms, [26][27][28][29] must be taken into account. Various systems employing these interactions, such as chiral assemblies, [21,[30][31][32][33] post-assembly manipulation, [34][35][36][37] and porous networks, [2,17,38] have recentlyb een intensively investigated by many groups.…”

Coadsorption of TbIII–Porphyrin Double-decker Single-molecule Magnets in a Porous Molecular Network: Toward Controlled Alignment of Single-molecule Magnets on a Carbon Surface

“…Tb III (OEP) 2 radicals and DBA-OC8 were synthesized by previously reported procedures. 14,30 Details of STM measurements are described in Supporting Information. First the solution of DBA-OC8 in 1-phenyloctane (20¯L, 3.7 © 10 ¹5 M) was drop-cast on HOPG (5 © 5 mm 2 ), and the 2D structures at the solid/liquid interface were observed by STM to ensure the formation of a porous network of DBA (Figure 2a).…”

“…First the solution of DBA-OC8 in 1-phenyloctane (20¯L, 3.7 © 10 ¹5 M) was drop-cast on HOPG (5 © 5 mm 2 ), and the 2D structures at the solid/liquid interface were observed by STM to ensure the formation of a porous network of DBA (Figure 2a). 30 The concentration of the DBA-OC8 solution was maintained at 3.7 © 10 ¹5 M for all subsequent experiments. After observing the hexagonal structure of DBA-OC8 on HOPG (Figure 2a The dependence on concentration of the pore occupation ratio containing bright spots over the entire sample area (100 © 100 nm 2 ) is summarized in Figure 3.…”