Nerea Bilbao

• PhD
• PostDoc Position at KU Leuven

We report on the fast reaction kinetics of an imine based 2D polymer (2DP) formed from a single monomer carrying both aldehyde and amine groups. Our results point towards a direct monomer-to-crystalline polymer transition without an amorphous intermediate.

This chapter provides a survey of the progress made in the construction of complex multicomponent supramolecular architectures on solid surfaces. The discussion is focussed on the self-assembly of organic building blocks physisorbed on solid surfaces such as graphite and gold and characterised using scanning tunnelling microscopy (STM). The fundame...

Graphene nanoribbons (GNRs), quasi-one-dimensional strips of graphene, exhibit a nonzero bandgap due to quantum confinement and edge effects. In the past decade, different types of GNRs with atomically precise structures have been synthesized by a bottom-up approach and have attracted attention as a novel class of semiconducting materials for appli...

The design and production of the next generations of synthetic aqueous self-assembled systems able to mimic some biological features will require increasingly sophisticated monomer constituents that make use of additional interactions to hydrophibic effects to attain enhanced structural and functional complexity. Here, we broadly investigate the aq...

Carbocatalysis holds a privileged position as a sustainable alternative to metal-based catalysis. While the focus in solution-based catalytic processes generally lies on how the heterogeneous catalyst affects the solution composition, more attention has recently been given to the analysis of the carbon material itself. Various outstanding surface c...

We report a crystalline supramolecular framework assembled by H-bonding interactions between covalently fused monomers equipped with two guanine-cytosine nucleobase pairs.

G4 on the floor: The unprecedented K⁺ G‐quartet has been detected as a transient intermediate along the course of G‐quadruplex self‐assembly following an approach that is reminiscent of classical covalent mechanistic studies. Abstract In analogy to covalent reactions, the understanding of noncovalent association pathways is fundamental to influenc...

In analogy to covalent reactions, the understanding of noncovalent association pathways is fundamental to influence and control any supramolecular process. Following an approach that is reminiscent of covalent methodologies, we study here, for the first time, the mechanism of G‐quadruplex formation in organic solvents. Our results support a reactio...

Synthetic two-dimensional polymers (2DPs) obtained from well-defined monomers via bottom-up fabrication strategies are promising materials that can extend the realm of inorganic 2D materials. The on-surface synthesis of such 2DPs is particularly popular, however the pathway complexity in the growth of such films formed on solid surfaces is poorly u...

A Scanning Tunneling Microscopy Study on Surface-Supported Imine-Based Covalent Organic Frameworks: a New Design for Robust 2D Materials. - Volume 25 Supplement - Nerea Bilbao, Deepali Waghray, Thijs Janssen, Steven De Feyter

In this communication, we report the first synthesis of structurally well-defined GNRs functionalized with dendritic polymers. The resultant GNRs possess grafting ratios of 0.59-0.68 for the dendrons of different generations. Remarkably, the precise 3D branched conformation of the grafted dendrons affords the GNRs unprecedented 1D supramolecular se...

Halogen bonding has emerged as a promising tool in two-dimensional (2D) crystal engineering. Since halogen bonds are similar to hydrogen bonds in a number of aspects, the existing knowledge of hydrogen bonded systems can be applied to halogenated systems. Here we evaluate the applicability of a retrosynthetic approach based on topological similarit...

We investigate the effect of covalently modified graphitic surfaces on the formation of single-layer covalent organic frameworks (sCOFs) at the solid-liquid interface. The impact of different densities of grafted aryl species was tested on the on-surface synthesis of three distinct imine-based 2D-sCOFs. The grafted aryl species that act as defects...

Supramolecular ring vs chain equilibria are ubiquitous in biological and synthetic systems. Understanding the factors that decide whether a system will fall into one side or the other is crucial to control molecular self‐assembly. Here, we report our results with two kinds of dinucleoside monomers in which the balance between closed cycles and open...

Bottom-up synthesis of low-bandgap graphene nanoribbons with various widths is of great importance for their applications in electronic and optoelectronic devices. Here we demonstrate a synthesis of N = 5 armchair graphene nanoribbons (5-AGNRs) and their lateral fusion into wider AGNRs, by a chemical vapor deposition method. The efficient formation...

We present an approach that makes use of DNA base pairing to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guests.

We present an approach that makes use of DNA base pairing to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guests.

Herein, we analyze the intrinsic chelate effect that multipoint H-bonding patterns exert on the overall energy of dinucleoside cyclic systems. Our results indicate that the chelate effect is regulated by the symmetry of the H-bonding pattern, and that the effective molarity is reduced by about three orders of magnitude when going from the unsymmetr...

Cyclization into closed assemblies is the most recurrent approach to realize the noncovalent synthesis of discrete, well-defined nanostructures. This review article particularly focuses on the noncovalent synthesis of monocyclic hydrogen-bonded systems that are self-assembled from a single molecule with two binding-sites. Taking advantage of intram...

A series of lipophilic nucleobases that are substituted at the 5- (pyrimidines) or 8- (purines) position with either a halogen atom or a terminal triple bond have been synthesized. The sequences and reactions studied in this work, which mainly comprise halogenation, alkylation, Sonogashira coupling, and trimethylsilylacetylene deprotection, have be...

A hydrogen‐bonded cyclic tetramer is assembled with remarkably high effective molarities from a properly designed dinucleoside monomer. This self‐assembled species exhibits an impressive thermodynamic and kinetic stability and is formed with high fidelities within a broad concentration range. Fine design of a dinucleoside monomer leads to hydrogen‐...

A series of lipophilic nucleosides comprising natural and non-natural bases that are pi-conjugated to a short oligophenylene-ethynylene fragment has been synthesized. These bases comprise guanosine, isoguanosine, 2-aminoadenosine as purine heterocycles, and cytidine, isocytosine and uridine as complementary pyrimidine bases. The hydrogen-bonding di...

The application of phosphinite–thioglycosides and phosphine–thioglycosides ligands in Rh(I)-catalyzed 1,4-addition of phenylboronic acid to cyclohexenone is reported. Among the ligands tested, phosphinite–thioglycoside 3 and phosphine–thioglycoside 10, bearing a 1,2-cis arrangement of the two heteroatoms, have exhibited the best results in terms of...