Orthogonal Insertion of Lanthanide and Transition‐Metal Atoms in Metal–Organic Networks on Surfaces

Abstract

Abstract:The orthogonal coordinative properties of tetrapyrrole macrocycles and nitrile ligands have been used in amultistep procedure towards interfacial d-f hetero-bimetallic nanoarchitectures based on af ree-base porphyrin derivative functionalized with meso-cyanobiphenylene substituents.M olecular-level scanning tunneling microscopystudies reveal that the porphyrin module alone self-assembles on Ag(111) in aclosepacked layer with asquare unit cell. Upon co-deposition of Gd atoms,asquare-planar motif is formed that reflects the fourfold coordination of CN ligands to the rare-earth centers.T he resulting nanoporous network morphology is retained following exposure to ab eam of Co atoms,w hichi nduces selective porphyrin metalation and ultimately yields ag ridlike 2D metallosupramolecular architecture.

Bicomponent Supramolecular Architectures at the Vacuum–Solid Interface

“…As described before, most of the studies take advantage of s-, d-, and p-metal (Na, K, Cs, Mn, Fe, Co, Ni, Cu, Ag, Au, Pb…) adatoms to bind molecular linkers. Recently, new species of adatoms have been used, namely, the lanthanides: cerium, 334 gadolinium, 335,336,337 and europium. 338 This case involves the formation of a bicomponent system composed of quarterphenyl-4,4"-dicarbonitrile and PTpy ligands.…”

Supramolecular Spangling, Crocheting, and Knitting of Functionalized Pyrene Molecules on a Silver Surface

“…In recent years, our groups and others have shown that programming organic molecules, through an appropriate geometrical combination of different peripheral recognition moieties, allows the formation of nanostructured surfaces featuring different architectures with various shapes and dimensions. [23][24][25][26][27][28] For example, exploiting the aptitude of pyridyl and cyanophenyl groups to engage in H-bonding, dipole-dipole or metal coordination interactions interactions, [29][30][31][32][33] functional porphyrin derivatives [34][35] featuring programmed geometries could be selectively organized in the presence of metal atoms as supramolecular polymers, 36 discrete macrocycles 37 or arrays with one 38 or two metal atoms. 31 In this context, photoactive polycyclic aromatic hydrocarbons (PAHs) are also of great interest due to their relevance in molecular electronics and photovoltaics.…”

“…[23][24][25][26][27][28] For example, exploiting the aptitude of pyridyl and cyanophenyl groups to engage in H-bonding, dipole-dipole or metal coordination interactions interactions, [29][30][31][32][33] functional porphyrin derivatives [34][35] featuring programmed geometries could be selectively organized in the presence of metal atoms as supramolecular polymers, 36 discrete macrocycles 37 or arrays with one 38 or two metal atoms. 31 In this context, photoactive polycyclic aromatic hydrocarbons (PAHs) are also of great interest due to their relevance in molecular electronics and photovoltaics. [39][40][41] Among the different PAHs, pyrene derivatives 42 have yet again renewed the interest of the scientific community as they constitute a suitable class of functional molecules for engineering optoelectronic devices [43][44] due to their synthetic versatility 42,[45][46] and strong emissive properties 42,47 Specific pyrene functionalizations were introduced to promote their self-assembly abilities and to tailor the interaction with carbon supports in solution, including nanotubes, graphene and HOPG.…”

Liquid-interface-assisted synthesis of covalent-organic and metal-organic two-dimensional crystalline polymers

“…One early representative work was reported by Talham et al in 2002, 31 who synthesized a crystalline ironnickel cyanide-bridged network by polymerization of amphiphilic pentacyanoferrate(III) complexes and iron ions at the air/water interface in a LB trough. Following this LB method, Kitagawa et al reported the synthesis of a monolayer 2D MOF comprising [5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin]cobalt (II) (E1) ligands and paddle-wheel linkages ( Fig. 2e) with two Cu 2+ and four COO − groups in 2010.…”

“…On the one hand, pioneering works on 2D poly(m-phenylene), covalent assemblies of porphyrin and thiophene, dynamic covalent polyimine networks, and metal-organic networks have been reported via the on-surface synthesis. [10][11][12][13][14][15] However, the mobility of monomers on the surface is limited and only small domain sizes have been obtained. Moreover, a transfer of such metal surfacebinding polymer networks is a complicated issue.…”