Homochirality is essential to many biological systems, and plays a pivotal role in various technological applications. The generation of homochirality and an understanding of its mechanism from the single-molecule to supramolecular level have received much attention. Two-dimensional chirality is a subject of intense interest due to the unique possibilities and consequences of confining molecular self-assembly to surfaces or interfaces. Here, we report the perfect generation of two-dimensional homochirality of porous molecular networks at the liquid-solid interface in two different ways: (i) by self-assembly of homochiral building blocks and (ii) by self-assembly of achiral building blocks in the presence of a chiral modifier via a hierarchical structural recognition process, as revealed by scanning tunnelling microscopy. The present results provide important impetus for the development of two-dimensional crystal engineering and may afford opportunities for the utilization of chiral nanowells in chiral recognition processes, as nanoreactors and as data storage systems.

We have studied the formation of stripe patterned films of ordered particle arrays on completely solvophilic substrates by using a self-organization technique. In this method, a substrate immersed in a suspension is withdrawn vertically at a controlled temperature. We have also systematically examined the effects of several experimental parameters. Well-defined stripes spontaneously form at the air-solvent-substrate contact line because of a very dilute suspension in a quasi-static process. The stripe width depends on particle concentration, withdrawal rate, and surface tension, while the stripe spacing depends on the thickness of stripes, surface tension, and type of substrate. A stripe width and the adjacent spacing show a clear correlation, strongly indicating the synchronized formation of a stripe and the next spacing. The evaporation rate does not affect stripe width and spacing but determines the growth rate of stripe patterned films. Based on these results, we propose a new mechanism for stripe formation, which is neither a stick-slip motion of the contact line nor dewetting but a negative feedback of particle concentration caused by a concavely curved shape of the meniscus, demonstrating not only its qualitative but also its quantitative validity.

With the use of a single building block, two nanoporous patterns with nearly equal packing density can be formed upon self-assembly at a liquid-solid interface. Moreover, the formation of both of these porous networks can be selectively and homogenously induced by changing external parameters like solvent, concentration, and temperature. Finally, their porous properties are exploited to host up to three different guest molecules in a spatially resolved way.

Multifunctional π-expanded macrocyclic oligothiophene 6-mer 1, as well as 9- (2) and 12-mers (3), was synthesized using a McMurry coupling reaction as the key step. The 6-mer 1 was converted to cyclo[6](2,5-thienylene-ethynylene) (4) by using a bromination-dehydrobromination procedure. From X-ray analysis, the crystal structures of nonplanar 1 and round-shaped 2 and 4 were elucidated. STM showed that 4 formed a self-assembled monolayer at the liquid/solid interface to produce a hexagonal porous network. Chemical oxidation of 1, 2, and 4 with 1 and 2 equiv of Fe(ClO4)3 produced 1(•+) and 1(2+), 2(•+) and 2(2+), and 4(•+) and 4(2+), respectively. Although oligothiophene radical cations containing β,β-disubstituted thiophenes usually do not form π-dimers, 4(•+) clearly formed a π-dimer owing to its planar, round shape. As for the dications of 1, 2, and 4, 1(2+), which has 34π-electrons, exhibited a large diatropic ring current effect, whereas 34π dication 4(2+) only showed a medium diatropic ring current effect. In contrast to 1(2+) and 4(2+), 52π dication 2(2+) had biradical cationic character instead of Hückel-type cyclic conjugation. Interestingly, 6-mer 1 showed polymorphism and unusual melting point behavior due to the number of stable conformations in the solid state. Single crystals of 1 melted at 176 °C, whereas an amorphous film of 1 crystallized in the temperature range of 80-83 °C to form a lamellarly stacked microcrystalline film, which melted at 139 °C. The polymorphism of 1 was applied to either fluorescence switching or switching of field effect transistor (FET) activity and electrical conductivity.