Intitulé du sujet: Engineering on-surface metal-molecule coordination at the sub-molecular level by STM

Sujet

Codirection: Dr. Xiaonan SUN

Nombre de mois: 48 mois

Ecole Doctorale: ED 388 - Chimie physique et Chimie analytique de Paris centre

Unité de recherche et équipe:

ITODYS, UMR 7086, Université Paris Cité (Paris 7)

l' équipe Nanoelectrochimie et electronique moleculaire

Coordonnées de l’équipe:

Prof. Jean Christophe Lacroix, chef d'equipe

Secteur: Sciences Physiques et Ingénierie / Physical sciences and Engineering

Langue attendue: Anglais

Niveau de langue attendu: C1

Description

Description du sujet:

The engineering of molecular self-organization on surface, followed by an in situ generation of different on-surface self-assemblies are of great scientific interest for the design and the invention of novel two dimensional (2D) nanomaterials. When metal ions are introduced to the preformed supramolecular self-assemblies, an important scientific question lies in how the molecular building blocks interact between them and then how they can coordinate with various metal ions on surface. The objective of this research project is using Scanning tunneling microscope characterization; the intermolecular binding leading to nanoscale re-organization which will be directly generated, visualized and then interpreted novel coordination at a sub-molecular scale with the presence of a surface.   

In this PHD program, a few well addressed organic building blocks will be used to investigate different surface supported metal-organic coordination. Several types of intermolecular interactions such as different kinds of hydrogen bonding and metal-ligand coordination bonding will be employed to tailor the surface organizations.  

• Elucidate intermolecular interactions driving molecular self-assemblies
• Vary surface organizations using variable molecular backbone shapes
• create metal-coordinated organic material by mixing molecules and variable metal ions

The main scientific objective of the project will be: 1) To understand and to control molecular assembly 2) to generate in situ metal-coordinated organic nanoarchitectures and investigate how the different metal coordination centers can influence the molecular assembly.

State of the Art: On-surface reactivity such as metal-molecule coordination  [1-12]  is a very rapidly developing field  complementing that of on surface supramolecular self-assembly. The presence of a surface makes coordination more versatile and highly interesting because several factors, such as the design of the molecular precursors, the variable metal ions, the versatility of chemical conditions, particularly the presence of the surfaces, can largely modify the chemical outputs. The added intermolecular/molecular-surface interaction and the specific environment under the microscope make engineering of the reaction and the following surface characterization very challenging.[1-15].

Surface coordination has been insensitively studied inside UHV environment in the past decade by famous STM groups such as Barth, Kern and Edjia, etc. The clean environments allow good control of molecular deposition to coordinate with metal atoms where an extra stimulus such as heat is often required. In our experiments, the advantage of working at the solid/liquid interface is that, not only complex molecules can be more easily deposited, but a large variety of different mono-, di- or trivalent metal ions can be introduced, for example Cu(I) or Cu(II), Fe(II) or Fe(III), etc. For the same ligand, variation of the metal ions or even their oxidation states can give new coordination configurations.   Very recently, few groups including the PI, succeeded with a novel approach in generating on surface intermolecular interactions at the solid liquid interface. The PI has reported in generating surface supported metal-coordination reactions by introducing Co(II) and Cu(II) metal ions into the pre-formed bipyridine terminated molecular self-assemblies. The strategy, to automatically form metal-molecule coordination using the active metal ions, provides wide opportunity to study different kinds of chemical reactions or coordination at the solid liquid interface. STM is a powerful technique capable of seeing molecules or to track chemical reactions at a sub-molecular level, will be used as a main characterization tool for this phd project.

Description of the tasks: The general scientific objectives of the scientific project are to generate and to visualize the reorganization generated by the reactions. The formation of metal coordinated at the solid/liquid interface, will be interpreted following the high resolution STM images which will provide deep insight of intermolecular interactions:

Task 1: Linear shape bpy-X-bpy molecules will coordinate with different metal ions:

The bpy-X-bpy molecule will be first organized on a surface by self-assembled processes. Molecules bearing bi-pyridine terminal groups linked by bridges with different functionalities can self-assembly at the solid-liquid interface and form ordered supramolecular self-organizations as depicted in Figure 1a. By introducing different metal ions, such as Co, Cu(I), Cu(II), Fe(II), Fe(III), Pt, Ag, ect; on surface reaction can be triggered where polymers of coordination can be successfully formed. Figure 1b shows a long linear Co-pyridine polymer formed and observed by STM. By changing the metal ions, different coordination frameworks will be generated on surface and will be investigated in this task.

Task 2: triangular or star shape molecules with pyridine terminals will coordinate with metal ions:

The variation of molecular backbones from a simple linear shape to more complex triangular or star shapes can play important roles to modify the metal coordinated frameworks as well as the intermolecular interaction and metal-molecule coordination configurations. The triangular skeletons have more chance to form porous coordination polymers which will be directly visualized by STM and will then be interpreted. At least two publications are expected.

The scientific products of the tasks are expected to give novel coordination configurations with the influence of the surface which will enrich the knowledge of 2D coordination chemistry from a fundamental point of view.

Methodology and Agenda:

The STM setups in ITODYS are running a very successful operation with good sensitivity in the past years. Well-designed ligands with active pyridine terminals (already available or will be synthesized by organic chemists through well-establish collaboration) will be mixed with typical metal ions where various on surface coordination will be studied by STM imaging at a sub-molecular resolution. Six month will be necessary to understand and to obtain enough results for a first publication. The following steps will be to modify the coordination frameworks by involving molecules with different central backbones. Different coordination configurations are expected by the variation of molecules as well as metal ions. Special care will need to be put in the specific experimental conditions to introduce different metal ions under STM environments.

References:

(1)        X. Sun*; X.Yao; F. Lafolet; G. Lemercier; J. C. Lacroix. One-Dimensional Double Wires and Two-Dimensional Mobile Grids: Cobalt/Bipyridine Coordination Networks at the Solid/Liquid Interface. J. Phys. Chem. Lett. 2019 10 (15), 4164-4169.

(2)         I. Hnid; X. Sun*; D. Frath; F. Lafolet; J. C. Lacroix. Multi-Functional Switches of Ditopic Ligands with Azobenzene Central Bridges. Nanoscale 2019, 11 (47), 23042.

(3)         X. Sun*; D. Frath; F. Lafolet; J. C. Lacroix. Supramolecular Networks and Wires Dominated by Intermolecular BiEDOT Interactions. J. Phys. Chem. C 2018, 122 (39), 22760–22766.

(4)       X. Sun*; J. C. Lacroix et al Molecular Isomerization and Multiscale Phase Transitions of a Ditopic Ligand on a Surface. J. Phys. Chem. C 2017, 121, 20925-20930.

(5)         X. Sun*; X. Yao; G. Trippé-Allard ; J. C. Lacroix. On-Surface Dimerization and Coordination of 4-(Bis-ethylenedioxythiophene) benzoic Acid, J. Phys. Chem. C 2021, 125, 957-963.

(6)         V. Q. Nguyen; X.Sun*; F.Lafolet; J. F.Audibert; F. Miomandre; G.Lemercier; F.Loiseau; J. C. Lacroix*. Unprecedented Self-Organized Monolayer of a Ru(II) Complex by Diazonium Electroreduction. J. Am. Chem. Soc. 2016, 138 (30), 9381–9384.

(7)       I.  Hnid, L. Guan, E. Chatir, S. Cobo, F. Lafolet, F. Maurel, J.C. Lacroix, X. Sun*,  Visualization and Comprehension of Electronic and Topographic Contrasts on Cooperatively Switched Diarylethene-Bridged Ditopic Ligand,  Nanomaterials  2022, 12 (8), 1318

(8)       L. Guan, F. Palmino, J.C. Lacroix, F. Chérioux, X. Sun*, [2+ 2] Cyclo-Addition Reactions for Efficient Polymerization on a HOPG Surface at Ambient Conditions, Nanomaterials 2023, 12 (8), 1334.

(9)       F. Silly, C. Dong, F. Maurel, X. Sun*, Two-Dimensional Hetero-to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives, Nanomaterials 2023, 13 (16), 2304.

(10)        Z. Chen, A. Narita, and K. Müllen, Adv. Mater. 2020, 2001893                                             

(11)    A. Narita, X. Y. Wang, X. L. Feng, K. Müllen, Chem. Soc. Rev. 2015, 44, 6616.

(12)     Y. Q.  Zhang, M, Ruben, J. V. Barth et al, Nature Communications  2012, 3, 1286.

(13)     S. Tebi, J. V. Barth, W. Schöfberger, S. Müllegger. ACS Nano 2017, 11, 3, 3383–3391.

(14)     N. Bilbao, K. S. Mali, and S. De Feyter. ACS Nano 2020, 14, 2, 2354–2365.

(15)     N. Kalashnyk, K. Mouhat, S. Clair et al, Nature Communications 2017, 8, 14735.

Compétences requises:

The idea candidate should have a physical chemistry background. Formations or trainings such as coordination chemistry, near field microscopy or surface functionality will be important experiences to fulfill the request of the project.

Références bibliographiques:

(1)        X. Sun*; X.Yao; F. Lafolet; G. Lemercier; J. C. Lacroix. One-Dimensional Double Wires and Two-Dimensional Mobile Grids: Cobalt/Bipyridine Coordination Networks at the Solid/Liquid Interface. J. Phys. Chem. Lett. 2019 10 (15), 4164-4169.

(2)         I. Hnid; X. Sun*; D. Frath; F. Lafolet; J. C. Lacroix. Multi-Functional Switches of Ditopic Ligands with Azobenzene Central Bridges. Nanoscale 2019, 11 (47), 23042.

(3)         X. Sun*; D. Frath; F. Lafolet; J. C. Lacroix. Supramolecular Networks and Wires Dominated by Intermolecular BiEDOT Interactions. J. Phys. Chem. C 2018, 122 (39), 22760–22766.

(4)       X. Sun*; J. C. Lacroix et al Molecular Isomerization and Multiscale Phase Transitions of a Ditopic Ligand on a Surface. J. Phys. Chem. C 2017, 121, 20925-20930.

(5)         X. Sun*; X. Yao; G. Trippé-Allard ; J. C. Lacroix. On-Surface Dimerization and Coordination of 4-(Bis-ethylenedioxythiophene) benzoic Acid, J. Phys. Chem. C 2021, 125, 957-963.

(6)         V. Q. Nguyen; X.Sun*; F.Lafolet; J. F.Audibert; F. Miomandre; G.Lemercier; F.Loiseau; J. C. Lacroix*. Unprecedented Self-Organized Monolayer of a Ru(II) Complex by Diazonium Electroreduction. J. Am. Chem. Soc. 2016, 138 (30), 9381–9384.

(7)       I.  Hnid, L. Guan, E. Chatir, S. Cobo, F. Lafolet, F. Maurel, J.C. Lacroix, X. Sun*,  Visualization and Comprehension of Electronic and Topographic Contrasts on Cooperatively Switched Diarylethene-Bridged Ditopic Ligand,  Nanomaterials  2022, 12 (8), 1318

(8)       L. Guan, F. Palmino, J.C. Lacroix, F. Chérioux, X. Sun*, [2+ 2] Cyclo-Addition Reactions for Efficient Polymerization on a HOPG Surface at Ambient Conditions, Nanomaterials 2023, 12 (8), 1334.

(9)       F. Silly, C. Dong, F. Maurel, X. Sun*, Two-Dimensional Hetero-to Homochiral Phase Transition from Dynamic Adsorption of Barbituric Acid Derivatives, Nanomaterials 2023, 13 (16), 2304.

(10)        Z. Chen, A. Narita, and K. Müllen, Adv. Mater. 2020, 2001893                                             

(11)    A. Narita, X. Y. Wang, X. L. Feng, K. Müllen, Chem. Soc. Rev. 2015, 44, 6616.

(12)     Y. Q.  Zhang, M, Ruben, J. V. Barth et al, Nature Communications  2012, 3, 1286.

(13)     S. Tebi, J. V. Barth, W. Schöfberger, S. Müllegger. ACS Nano 2017, 11, 3, 3383–3391.

(14)     N. Bilbao, K. S. Mali, and S. De Feyter. ACS Nano 2020, 14, 2, 2354–2365.

(15)     N. Kalashnyk, K. Mouhat, S. Clair et al, Nature Communications 2017, 8, 14735.