About
153
Publications
16,262
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
2,395
Citations
Publications
Publications (153)
Tuning the synthesis of quinoxaline derivatives toward a new family of azamacrocycles.
On-surface synthesis under ultra-high vacuum (UHV) conditions facilitates the fabrication of unique molecular compounds, replicating established in-solution protocols. However, the intramolecular hydroamination and cyclization (IHC) of alkynes on surfaces remain...
This work focuses on the development of nickel‐based quinone complexes as electrode materials for next‐generation rechargeable batteries. These complexes were synthesized with different substituents and their potential as anode materials in lithium‐based systems was investigated. Scanning electron microscopy (SEM) and energy‐dispersive X‐ray spectr...
This review provides a comprehensive examination of the applications of the seminal coupling principle introduced by Siegfried Dähne and Dieter Leupold in 1966. Their heuristic and groundbreaking work proposed that combining multiple polymethine subunits within a single chromophore enables orbital coupling, consequently narrowing the HOMO–LUMO gap,...
Temperature is an essential physical characteristic that influences all biological processes. Building on previous research on dialkylamino-functionalized rhodamine-based thermo-sensors, we investigate herein the thermosensitive properties of triamino-phenazinium dyes. Through a simple five-step synthetic route, we synthesized amino-phenazinium chr...
Two new benzobisimidazole platforms incorporating 7-hydroxyquinoline moieties were synthesized and characterized to explore potential multiple proton transfer processes. Combining experimental analysis with theoretical insights, we investigated the photophysical properties and...
This study presents the synthesis and characterization of phenazinium dyes with absorption ranging from red to far-red, as well as emission extending into the far-red to near-infrared (NIR) region. The procedure involves the post-functionalization of a triamino-phenazinium that was recently reported as a theranostic agent. The introduction of elect...
Since the introduction of hybrid van der Waals heterostructures (h-vdWHs) for device architecture development, many vertically staked organic two-dimensional materials have been investigated in order to control transport properties. This article introduces a novel h-vdWH that achieves periodic interaction by the development of a superlattice. We de...
Precise control of multiple spin states on the atomic scale presents a promising avenue for designing and realizing magnetic switches. Despite substantial progress in recent decades, the challenge of achieving control over multiconfigurational reversible switches in low-dimensional nanostructures persists. Our work demonstrates multiple, fully reve...
A solventless and acid-catalyzed condensation of meso-perfluoroalkyl-dipyrromethanes on selected benzaldehydes was used to prepare ten different bilanes that were isolated before their oxidation into trans-A2B-corroles bearing two meso-perfluoroalkyl groups. Macrocyles...
The synthesis of N-fused heterocycles is a crucial element in organic chemistry. However, it involves multiple steps that add complexity and reduce overall yields. Here, we introduce the high-yield on-surface synthesis of N-heterocyclic compounds employing the intramolecular hydroamination of alkyne-functionalized molecular precursors under mild th...
Tetraamino-tetranitro-azacalixarene 5 is at the crossroad of two different families of compounds depending on the conditions and the agent used to reduce the NO2 groups: (1) azacalixphyrin 7 in neutral medium, or (2) phenazinium of type 8 in acidic medium. The key role of the N-substituted amino functions at the periphery is highlighted by investig...
A series of heptamethine-oxonol dyes featuring different heterocyclic end groups were designed with the aim to explore structure-properties relationships in π-extend coupled polymethines. These dyes can be stabilised under three different
protonation states, affording dicationic derivatives with an aromatic core, cationic heptamethines, and zwitte...
Previously, we reported a guest molecule containing a viologen (V), a phenylene (P) and an imidazole (I) fragment (VPI) forming a host : guest 2 : 2 complex with cucurbit[8]uril (CB[8]) and an unprecedented 2 : 3 complex with cucurbit[10]uril (CB[10]). To better address the structural features required to form these complexes, two VPI analogues wer...
A near‐infrared‐absorbing heptamethine (HM⁺) incorporating three bulky benzo[cd]indole heterocycles was designed to efficiently prevent self‐aggregation of the dye, which results in a strong enhancement of its photoinitiating reactivity as compared to a parent bis‐benzo[cd]indole heptamethine (HMCl⁺) used as a reference system. In this context, we...
Efficient enzyme immobilization is crucial for the successful commercialization of large-scale enzymatic water treatment. However, issues such as lack of high enzyme loading coupled with enzyme leaching present challenges for the widespread adoption of immobilized enzyme systems. The present study describes the development and bioremediation applic...
A near‐infrared‐absorbing heptamethine (HM+) incorporating three bulky benzo[cd]indole heterocycles was designed to efficiently prevent self‐aggregation of the dye, which results in a strong enhancement of its photoinitiating reactivity as compared to a parent bis‐benzo[cd]indole heptamethine (HMCl+) used as a reference system. In this context, we...
The straightforward access to N- or C-substituted dinitro-tetraamino-phenazines (P1-P5) is enabled in oxidative conditions via formation of two intermolecular C-N bonds from accessible 5-nitrobenzene-1,2,4-triamine precursors. The photophysical studies revealed green absorbing and orange-red emitting dyes, with enhanced fluorescence in the solid st...
The structure of the Viologen‐Phenylene‐Imidazole (VPI) guest, previously shown to be bound by cucurbit[7]uril (CB[7]) with binding modes depending on pH and silver ions, has been extended by adding hydrophobic groups on the two extremities of VPI before investigations of CB[7] binding by NMR, ITC, X‐ray diffraction, UV‐vis and fluorescence spectro...
Azacalixphyrins are used as building blocks to elaborate nanostructures with different shapes depending on the nature of the N-substituents. In this work, the formation of nanoribbons from N-alkyl azacalixphyrin 4, and nanodonuts from the N-aryl analogue 5, is presented and rationalized by molecular dynamics (MD) simulations. Indeed, MD revealed di...
Within the heteroacene family, azapentacenes have received much attention in organic electronic devices due to their unique physico-chemical properties. This is particularly true for the 5,14-dihydro-5,7,12,14-tetraazapentacene despite its poor solubility in organic solvents which logically hindered the study of its electrochemical behavior. Conseq...
Hybrid van der Waals heterostructures made of 2D materials and organic molecules exploit the high sensitivity of 2D materials to all interfacial modifications and the inherent versatility of the organic compounds. In this study, we are interested in the quinoidal zwitterion/MoS2 hybrid system in which organic crystals are grown by epitaxy on the Mo...
The last decade has seen a flurry of studies related to graphene nanoribbons owing to their potential applications in the quantum realm. However, little experimental work has been reported towards nanoribbons of other 2D materials. Here, we propose a universal approach to synthesize high-quality networks of nanoribbons from arbitrary 2D materials w...
Azacalix[n]arenes (ACAs) are lesser-known cousins of calix[n]arenes that contain amine bridges instead of methylene bridges, so they generally have higher flexibility due to enlarged cavities. Herein, we report a highly substituted cationic azacalix[4]arene-based covalent organic framework (ACA-COF) synthesized by the Zincke reaction under microwav...
2,5-Diamino-1,4-benzoquinonediimine (DABQDI) derivatives possessing two electron-withdrawing aromatic N-substituents can potentially exhibit a zwitterionic ground state in lieu of the expected canonical structure. It was previously shown that the use of nitroaromatics electron-withdrawing groups (EWG) could yield the quantitative formation of zwitt...
The on‐surface synthesis of metal‐organic covalent coordination networks with a dense Kagomé lattice of metallic centers is reported. Tetrahydroxyquinone and metal atoms (M = Cu or Mn) are codeposited on Ag(111) substrate to build well‐ordered 2D lattices M3C6O6. The surface is studied by scanning tunneling microscopy, low‐energy electron diffracti...
We predict two switchable one-dimensional (1D) spin-polarized semiconductors based on metal-organic coordination chains constructed out of Fe, V, and zwitterionic quinone (ZQ) molecules using first-principle density functional theoretical analysis. The Fe-ZQ coordination chain can be converted from a semiconductor to a half-metal when oxidized by c...
The last decade has seen a flurry of studies related to graphene nanoribbons owing to their potential applications in the quantum realm. However, little experimental work has been reported towards nanoribbons of other 2D materials due to the absence of synthesis routes. Here, we propose a universal approach to synthesize high-quality networks of na...
We report on the formation of a high-order commensurate (HOC) structure of 5,14-dihydro-5,7,12,14-tetraazapentacene (DHTAP) molecules on the highly corrugated Cu(110)-(2 × 1)O surface. Scanning tunnelling microscopy shows that the DHTAP molecules form a periodic uniaxial arrangement in which groups of seven molecules are distributed over exactly ni...
We report on the successful on-surface synthesis of metal-organic covalent coordination networks with a dense Kagome lattice of metallic centers. In the case of Mn centers ab-initio calculations show that the adsorbed monolayer on Ag(111) has all the characteristic features of a strictly two-dimensional (2D) ferromagnetic Kagome metal. Tetrahydroxy...
The development of methodologies to control on demand and reversibly supramolecular transformations from self‐assembled metalla‐structures requires the rational design of architectures able to answer to an applied stimulus. While solvent or concentration changes, light exposure or addition of a chemical have been largely explored to provide these t...
Azacalixphyrins are unique aromatic macrocycles featuring strong absorption from the visible to the near-infrared (NIR) spectral ranges. This work demonstrates through EPR spin-trapping experiments that the N-alkyl tetrasubstituted azacalixphyrin (ACP) can lead to the formation of carbon-centered radicals initiating for the free-radical photopolyme...
Dihydrotetraazapentacene molecules can be dehydrogenated on the surface to form tetraazapentacene by applying a high electric field between the tip of a scanning tunnelling microscope and a metallic substrate in the zero-current limit.
Starting from pyrrole-carbinol derivatives, a set of three optimized experimental conditions was used to prepare six dipyrromethanes (DPM) bearing meso-poly-halogeno-alkyl chains. On the one hand, the condensation of -anisaldehyde and the DPMs bearing a perfluoroalkyl chain (CF3, C3F7 or C7F15) produced, after oxidation, the expected trans-A2B2-por...
The electronic and magnetic properties of one-dimensional polymers of zwitterionic quinone (ZQ) molecules with 4d and 5d transition metals (TM) are studied using density functional calculations. We present the results of first-principle calculations for the electronic and magnetic properties, including the magnetic anisotropy energy (MAE) of select...
The interface between the semiconductor and the dielectric layer plays a crucial role in organic field-effect transistors (OFETs) because it is at the interface that charge carriers are accumulated and transported. In this study, four zwitterionic benzoquinonemonoimine dyes featuring alkyl and aryl N-substituents were used to cover the dielectric l...
Heat shock protein 27 (Hsp27) has an established role in tumor progression and chemo-resistance of castration-resistant prostate cancer (CRPC). Hsp27 protects eukaryotic translation initiation factor 4E (eIF4E) from degradation, thereby maintaining survival during treatment. Phenazine derivative compound #14 was demonstrated to specifically disrupt...
The first example of diamino-benzoquinonediimine bearing both electron-donating and electron-withdrawing groups on the same 6-π electron subunit was synthesized using a straightforward one pot strategy. Photophysical analysis and theoretical calculations demonstrate that this unique substitution pattern is efficient to favour the establishment of a...
Recently π–d conjugated coordination polymers have received a lot of attention owing to their unique material properties, although synthesis of long and defect‐free polymers remains challenging. Herein we introduce a novel on‐surface synthesis of coordination polymers with quinoidal ligands under ultra‐high vacuum conditions, which enables formatio...
Azacalixphyrins are bis-zwitterionic aromatic macrocycles that feature absorption properties in the near-infrared range. Their N-substitution is an efficient strategy for tuning the absorption maxima by stabilizing different tautomeric forms depending on the nature of the substituent (alkyl or aryl give 1-5 or 2-6 tautomers, respectively). This wor...
The transamination of oxoaminobenzoquinonemonoimine (BQI derivatives), an unconventional zwitterionic quinone, allows isolation of a series of compounds featuring electron-donating aryl auxochromes. The substitution has a very strong impact on the electrochemical and optical features, which is rationalized by theoretical calculations. Protonation a...
The on‐surface synthesis approach under UHV conditions has led us to the formation of 1D coordination π–d conjugated polymers on metal surfaces. The reaction of quinoidal ligand with different transition metals results in two distinct coordination motifs: four‐fold (Cr, Fe, Co, Ni) and two‐fold (Cu). The backbone of the Cu‐coordinated 1D chain is f...
In hydrogen bonded systems, nuclear quantum effects such as zero-point motion and tunneling can significantly affect their material properties through underlying physical and chemical processes. Presently, direct observation of the influence of nuclear quantum effects on the strength of hydrogen bonds with resulting structural and electronic implic...
We report the synthesis of a square-planar nickel complex in which the metal center is located in a NOON environment. Promoting its axial ligation triggers a spin state switching process which is accompanied by a change of the absorption properties depending on the solvent. Indeed, a strong solvatochromic shifts could be observed in the presence of...
We demonstrate that the conductance switching of benzo-bis(imidazole) molecules upon protonation depends on the lateral functional groups. The protonated H-substituted molecule shows a higher conductance than the neutral one (Gpro>Gneu), while the opposite (Gneu>Gpro) is observed for a molecule laterally functionalized by amino-phenyl groups. These...
We demonstrate that the conductance switching of benzo-bis(imidazole) molecules upon protonation depends on the lateral functional groups. The protonated H-substituted molecule shows a higher conductance than the neutral one (Gpro>Gneu), while the opposite (Gneu>Gpro) is observed for a molecule laterally functionalized by amino-phenyl groups. These...
On-surface polymerization of iron atoms and zwitterion quinone (ZQ) molecules on Ag(111) is studied experimentally under ultra-high vacuum and theoretically in the framework of density functional theory. The resulting one-dimensional (1D) polymer chain is a promising model system to study both magnetic and conductive properties in one dimension. Pr...
The fusion of two azacalixphyrin cycles absorbing in the NIR-I domain moves the absorption properties beyond 1000 nm, towards the second biological transparency window (NIR-II). The synthesis of this new...
In article number 1903816, Aleksandar Matković and co‐workers employ networks of self‐assembled organic nanostructures epitaxially grown on two‐dimensional hexagonal boron nitride. The work demonstrates how the polarization direction of external light can be used to realize a “light‐gate” for switching on and off the conductivity of organic nanocry...
An in-depth investigation of the optical properties of recently-synthesized linear azaacene derivatives of various electronic nature (neutral, dicationic, and zwitterionic) is presented. Our simulations include not only the determination of the vertical transitions, but also of the adiabatic energies and vibrationally-resolved spectra using the Adi...
The synthesis and properties of 1,2,3,4-tetrahydro-1,4,5,8-tetraazaanthracene (THTAA) – a heterocycle involving both >N–H donating and =N– accepting moieties – have been reinvestigated. Unlike previously reported, THTAA is a thermally stable compound that can be re-sublimed at 300–310 °C without decomposition. Controlled introduction of substituent...
Introducing organic semiconductors as additional building blocks into heterostructures of 2D materials widens the horizon of their applications. Organic molecules can form self‐assembled and self‐aligned crystalline nanostructures on 2D materials, resulting in well‐defined interfaces that preserve the intrinsic properties of both constituents. Thus...
The transamination reaction of 2,5-diaminobenzoquinonediimine (QDI) with ethylenediamine gave fluorescent 1,2,3,4-tetrahydropyrazino[2,3-g]quinoxaline (1). When the same reaction was carried out with N,N’-bis(aminoethyl)-1,3-propanediamine, a novel cationic quinoxalinium species (2) was isolated, which can be further condensed with p-cyanobenzaldeh...
The cover illustrates a new family of macrocycles, the azacalixquinarenes, which are built on quinoidal rings that can present either canonical or zwitterionic forms. The picturing of such electronic versatility would have been extremely arduous without the preliminary isolation of a single-crystal structure.
Azacalixquinarenes, a new family of macrocycles constituted of diaminobenzoquinone diimine units linked by dinitrobenzene rings are synthesized by selected oxidation of the parent azacalixarenes. Crystallographic analyses of two compounds demonstrated the presence of (uncharged) canonical and zwitterionic quinones within a single structure. The ele...
Near-infrared (NIR) azacalixphyrins bearing aryl substituents strongly impacting the physico-chemical properties of the macrocycles were designed, enabling hyperchromic and bathochromic shifts of the absorption compared to their N-alkylated analogues. This engineering enhances the photoacoustic response under NIR excitation, making azacalixphyrins...
We report the synthesis of a key mononuclear intermediate complex based on a quinoid ligand and its further metalation to afford the corresponding hetero-bimetallic compound that revealed unique properties. An unprecedented hetero-bimetallic effect in coordination chemistry could be indeed observed and exploited to prepare, through selective ligand...
Azacalixphyrin derivatives constitute one of the most intriguing class of macrocyclic compounds. Indeed, these isostructural and isoelectronic analogues of porphyrins intensively absorb light up to the near infrared region, exist under several tautomeric forms and present a bis-zwitterionic structure, with a central dianionic core surrounded by pos...
[This corrects the article DOI: 10.18632/oncotarget.20469.].
A series of N-substituted diamino-benzoquinone diimines featuring tunable aryl electron-withdrawing functions were synthesized. For the first time, the subtle variation of electronic richness allows to control the canonical vs zwitterionic equilibrium through the tuning of the intramolecular proton transfer. The establishment of a ground-state zwit...
The adsorption of 5,14-dihydro-5,7,12,14-tetraazapentacene (DHTAP) on Cu(110) has been investigated at different temperatures and coverages by means of scanning tunneling microscopy (STM) and low-energy diffraction (LEED). Our results show that the interaction of DHTAP with the Cu(110) surface differs considerably from that of pentacene on the same...
Dihydro-tetraaza-acenes are promising candidates for future applications in organic electronics, since these molecules form crystals through an interplay between H-bonding, dipolar, and van der Waals interactions. As a result, densely packed − π π structures – favorable for charge transport – are obtained, with exceptional stability under ambient c...
We present a combined experimental and theoretical study of electronic and optical properties of dihydro-tetraaza-acenes (DHTAn). Using a solvent-free condensation, we are able to synthesize not only DHTA5 but also the longer DHTA6 and DHTA7 molecules. We then investigate their gas-phase electronic structures by means of ab-initio density functiona...