Reversing the Handedness of Self‐Assembled Porous Molecular Networks through the Number of Identical Chiral Centres

Abstract

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Porous Self-Assembled Molecular Networks as Templates for Chiral-Position-Controlled Chemical Functionalization of Graphitic Surfaces

“…The three chiral chains are located at the rims of the hexagonal pores because of steric demands (Figure 8a,b). 57 Unit cell parameters are a = b = 3.2 ± 0.1 nm and γ = 60 ± 1°, which are identical to those of DBA-OC6. However, the angle α measures only negative values of −6.7 ± 0.8°, consistent with the homochirality of the network.…”

“…To create supramolecular template layers of unique handedness, a requisite for the formation of homochiral grafted patterns later on, we designed and synthesized DBA cDBA-OC6(S)-OC6, a chiral template molecule, having three chiral OC6(S) chains with methyl groups attached to stereogenic centers and three achiral OC6 chains. 41,57 Indeed, cDBA-OC6(S)-OC6 exclusively forms a CCW honeycomb structure at 1,2,4-trichlorobenzene (TCB)/graphite interface after annealing treatment at 80 °C for 5 h (2.0 × 10 −5 M, Figure S20). The three chiral chains are located at the rims of the hexagonal pores because of steric demands (Figure 8a,b).…”

Stereospecific Epitaxial Growth of Bilayered Porous Molecular Networks

“…40 We reported the formation of supramolecular networks of a well-defined handedness using chiral DBA (cDBA) molecules, such as cDBA-OC12(S) and cDBA-OC12(R) (Chart 1), with methyl-substituted stereogenic centers, and their roles in inducing and inversing supramolecular chirality of networks of achiral DBA molecules. [41][42][43] Based on these results, we hypothesized that replacing the methyl groups with hydrogen bonding groups would also lead to the formation of similar porous chiral networks, and furthermore would enforce the formation of porous multilayers (Scheme 1), even in a stereo-controlled manner. Scheme 1. a) Typical supramolecular pore formed by alkylated DBA molecules.…”