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.
Supramolecular self-assembly of suitably functionalized building blocks on surfaces can serve as an excellent test-bed to gain understanding and control over multicomponent self-assembly in more complex matter. Here we employ a powerful combination of scanning tunnelling microscopy (STM) and molecular modeling to uncover two-dimensional (2D) crystallization and mixing behavior of a series of alkylated building blocks based on dehydrobenzo[12]annulene, forming arrays of nanowells. Thorough STM investigation employing high-resolution spatial imaging, use of specially designed marker molecules, statistical analysis and thermal stability measurements revealed rich and complex supramolecular chemistry, highlighting the impact of odd-even effects on the phase behavior. The methodology and analysis presented in this work can be easily adapted to the self-assembly of other alkylated building blocks.
Opening light: Two‐dimensional pores are formed by the self‐assembly of azobenzene‐functionalized triangular building blocks on graphite at the liquid–solid interface. These pores can selectively host a guest molecule. The pore size can be reversibly changed by irradiation at different wavelength which changes the number of guest molecules that are adsorbed (see scheme).
Licht an, Poren auf: Zweidimensionale Poren werden durch Selbstorganisation von Azobenzol‐funktionalisierten dreieckigen Bausteinen an der Fest‐flüssig‐Grenzfläche auf Graphit gebildet. Die Poren können selektiv Gastmoleküle aufnehmen. Die Porengröße – und damit auch die Zahl der adsorbierten Gastmoleküle – lässt sich mit Licht unterschiedlicher Wellenlängen reversibel verändern (siehe Schema).
In the version of this Article originally published, a systematic error in converting the energies obtained by molecular mechanics calculations to the total energies used to evaluate the relative stabilities of the molecular network models, led to incorrect energy values being reported. The correct values are as follows:In 'Control of homochirality in a porous molecular network' , modelling of hexamers of cDBA-OC12-(S) CW structure was found to be 9.66 kcal mol −1 more stable than the CCW pattern.In 'Chiral induction in a porous molecular network' , the difference between CW and CCW hexamers formed by five molecules of DBA-OC12 and one of cDBA-OC12-(S) was found to be only 0.24 kcal mol −1 .In 'Hierarchical chiral induction mechanism' , for cyclic hexamers of one chiral cDBA-OC12-(S)-OC13-(R) and five achiral DBA-OC12 on graphite, the CW hexagonal structure is favoured by 3.88 kcal mol −1 . In comparison, in similar structures made from cDBA-OC12-(S)-OC13-(R) and DBA-OC13 the energy difference between the CW and CCW structures was only 1.33 kcal mol −1 .These errors do not affect the conclusions of the work, and all of the values have been corrected in the online versions of the Article.
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