Magic organic clusters, representing well-defined zero-dimensional organic clusters with identical sizes and configurations, have received increased interests in recent years. Previously, the magic clusters were mainly stabilized through van der Waals force, C–H...π interaction, hydrogen bonding, dipole interaction, etc., which yet lack thermal stability and tunable electronic transport properties for potential applications. The introduction of metal adatoms into the organic systems would be an excellent choice for facilitating more stable magic clusters as the metal adatoms could serve as a nucleation center and help for clustering of organic ligands with increased stabilities. Considering the limited coordination number of metal species, it would be of great interest to introduce multilevel interactions besides metal–organic bonding, which may provide new avenues for controllable fabrication of more complicated and larger magic clusters. Herein, we have achieved the controllable fabrication of three distinct magic metal–organic clusters, especially two hierarchical ones with different sizes on the reconstructed Au(111) and unreconstructed Ag(111) surface. The key for various unprecedented magic hierarchical clusters here is the selection of the organic ligands with only one active carboxyl (−COOH) group which possesses bonding flexibility and diversity features after dehydrogenation but avoids the usual two-dimensional network of those containing more −COOH groups.

Chiral molecular self‐assemblies were usually achieved using short‐range intermolecular interactions, such as hydrogen‐, metal–organic, and covalent bonding. However, unavoidable surface defects, such as step edges, surface reconstructions, or site dislocations may limit the applicability of short‐range chirality recognition. Long‐range chirality recognition on surfaces would be an appealing but challenging strategy for chiral reservation across surface defects at long distances. Now, long‐range chirality recognition is presented between neighboring 3‐bromo‐naphthalen‐2‐ol (BNOL) stripes on an inert Au(111) surface across the herringbone reconstruction as investigated by STM and DFT calculations. The key to achieving such recognition is the herringbone reconstruction‐induced local dipole accumulation at the edges of the BNOL stripes. The neighboring stripes are then forced to adopt the same chirality to create the opposite edged dipoles and neutralize the neighbored dipole moments.

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.202008036.Advanced fabrication of surface metal-organic complexes with specific coordination configuration and metal centers will facilitate to exploit novel nanomaterials with attractive electronic/magnetic properties. The precise on-surface synthesis provides an appealing strategy for in situ construction of complex organic ligands from simple precursors autonomously. In this paper, distinct organic ligands with stereo-specific conformation are separately synthesized through the well-known dehalogenative coupling. More interestingly, the exo-bent ligands promote the mono-iron chelated complexes with the Fe center significantly decoupled from the surface and of high spin, while the endo-bent ligands lead to bi-iron chelated ones instead with ferromagnetic properties.

Advanced fabrication of specific graphene analogs on surfaces will facilitate the exploitation of unexplored physical properties that may enrich their potential applications in the future, and the quest for graphene analogs has expanded from covalent graphene analogs to non-covalent ones. Previously, artificial non-covalent molecular graphene has been assembled by atomic manipulation, which, however, is a technical challenge and extremely limits the creation of non-covalent graphene analogs over a large area. Herein, we achieve the fabrication of a chlorine(Cl)-based non-covalent graphene analog stabilized by copper(Cu) adatoms on Cu(111) through an easy-to-facilitate self-assembly approach, as demonstrated by the combination of scanning tunneling microscopy imaging and density functional theory calculations. Moreover, the Cu adatoms are found to uniformly distribute within such a non-covalent graphene analog, which is inaccessible for covalent ones and shows potential for stabilizing the non-covalent graphene analog as well as modulating its overall electronic properties. Such findings exemplify the construction of non-covalent graphene analogs with a large area by a more effective self-assembled approach in contrast to the previous atomic manipulation method.

Chiral molecular self‐assemblies were usually achieved using short‐range intermolecular interactions, such as hydrogen‐, metal–organic, and covalent bonding. However, unavoidable surface defects, such as step edges, surface reconstructions, or site dislocations may limit the applicability of short‐range chirality recognition. Long‐range chirality recognition on surfaces would be an appealing but challenging strategy for chiral reservation across surface defects at long distances. Now, long‐range chirality recognition is presented between neighboring 3‐bromo‐naphthalen‐2‐ol (BNOL) stripes on an inert Au(111) surface across the herringbone reconstruction as investigated by STM and DFT calculations. The key to achieving such recognition is the herringbone reconstruction‐induced local dipole accumulation at the edges of the BNOL stripes. The neighboring stripes are then forced to adopt the same chirality to create the opposite edged dipoles and neutralize the neighbored dipole moments.