Self-sorting multiple building blocks for correctly positioning molecules through orthogonal recognition is a promising strategy for construction of a hierarchical self-assembled molecular network (SAMN) on a surface. Herein we report...

Scanning tunnelling microscope observations at the 1‐phenyloctane/graphite interface reveal how chiral structural information at the molecular level is transferred and expressed structurally at the 2D supramolecular level for a porous system. The chirality of self‐assembled molecular networks formed by chiral dehydrobenzo[12]annulene (cDBA) derivatives having three chiral chains and three achiral chains, alternatingly, is compared with those of cDBAs having six chiral chains reported previously. While for all cDBAs homochiral surfaces are formed, their handedness is not simply a reflection of the absolute configuration of the stereogenic centres. Both the number of stereogenic centres as well as the length of the achiral chains determine the supramolecular handedness, providing a deep insight into the supramolecular chirality induction mechanisms at play. Moreover, these cDBAs act to induce chirality in porous networks formed by achiral DBAs.

We herein investigated the effect of the number of alkoxy chains on the two-dimensional selfassembly of a trigonal molecular building block. To this end, a dehydrobenzo[12]annulene (DBA) derivative, DBA-OC14-OC1 having three tetradecyloxy chains and three methoxy groups in an alternating manner, was synthesized. Scanning tunneling microscopy (STM) observations at the 1,2,4-trichlorobenzene (TCB)/graphite interface revealed that DBA-OC14-OC1 forms three monolayer structures, porous honeycomb, parallelogram, and hexagonal A structures. At the 1phenyloctane (PO)/graphite interface, DBA-OC14-OC1 also forms three structures: parallelogram, hexagonal B and dense-linear structures. In contrast to the previously reported DBA derivative DBA-OC14 having six tetradecyloxy chains, DBA-OC14-OC1 shows structural polymorphism with a variety of alkyl chain interaction modes. Since in the observed patterns DBA-OC14-OC1 adopts a low symmetric Cs or C1 geometry, the variation of the interaction modes and the resulting network patterns likely originate from the conformational flexibility on surface of this DBA by decreasing number of alkyl chains. Molecular mechanics simulations gave insight in the structural and energy aspects of this pattern formation. We also discussed the role of solvents, TCB and PO, on the polymorph formation.

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