Two-dimensional Supramolecular Self-Assembling at Surfaces: - - PowerPoint PPT Presentation

Université Pierre et Marie Curie Paris 6

André-Jean ATTIAS andre-jean.attias@upmc.fr

Two-dimensional Supramolecular Self-Assembling at Surfaces: Engineering and Functionality for Nanotechnologies (nanophotonics, nanooptoelectronics).

OUTLINE 1 – How to Shape Matter Macro vs Nanoworld 2 – Supramolecular chemistry at Surfaces Supramolecular chemistry Supramolecular chemistry at surfaces STM 3 – 2D Supramolecular Self-Assembly Hydrogen bond interaction Metal ligand interaction Van der Walls interaction 4- Our Contribution From Molecular ‘Clip’ to 3D Janus Tecton

To carve the four presidential heads into the face of Mount Rushmore, Borglum utilized new methods involving dynamite and pneumatic hammers to blast through a large amount of rock quickly, in addition to the more traditional tools of drills and chisels. Some 400 workers removed around 450,000 tons of rock from Mount Rushmore, which still remains in a heap near the base of the mountain.

How to Shape Matter? By carving

To carve the four presidential heads into the face of Mount Rushmore, Borglum utilized new methods involving dynamite and pneumatic hammers to blast through a large amount of rock quickly, in addition to the more traditional tools of drills and chisels. Some 400 workers removed around 450,000 tons of rock from Mount Rushmore, which still remains in a heap near the base of the mountain.

By carving How to Shape Matter?

The entire project took about 23 years to complete, 2,300,000 building blocks, weighing an average of 2.5 tons each (Although some weigh as much as 16 tons) were used to build the great pyramid. The length of each side of the pyramid at the base is 755 feet (230.4 m). They rise at an angle of 51 52′ to a height, originally,

• f 481 feet (147 m) but nowadays 451 feet

(138 m).

By assembling How to Shape Matter?

How to Control Matter at the Nanoscale?

• What is Nanotechnology?

 Nanotechnology is an emerging set of tools, techniques and unique applications involving the structure and composition of materials on a nanoscale.  Nanotechnology aims to create and use structures, devices and systems in the size range of about 0.1–100 nm. (covering the atomic, molecular and macromolecular length scales). By manipulating matter at this length scale one hopes to achieve superior/new properties of these materials for applications in our macroscopic world.

Miniaturization

Semiconductor industry

Emerging needs

NANOTECHNOLOGY

µm- nm-

• ‘top-down’: lithography and printing

mature serial processes limited in sub-50 nm range

J.V. Barth et al. Nature, 2005, 437, 671

How to Control Matter at the Nanoscale?

• Use of 193 excimer laser with

phase shift masks to for features 65 nm in size.

• Phase shift masks and complex
• ptics are used to achieve this

resolution.

How to Control Matter at the Nanoscale?

• Lithography

resolution

• Extreme UV
• Electron-beam
• X-ray radiation

IBM Research

How to Control Matter at the Nanoscale?

Thermoplastic Nanoimprint lithography Photo Nanoimprint Lithography http://www.semiconductoronline.com/Content/ProductShowcase/ http://www.nanonex.com/Picture/Resists2.jpg

• Nanoimprint Lithography

How to Control Matter at the Nanoscale?

Soft and hard stamps are used to transfer patterns with feature sizes above 100 nm onto a wide range of substrates

• Multiphoton lithography?

(talk by Prof. Kwang Sup Lee, Korea France joint Symposium) How to Control Matter at the Nanoscale? What do you think?

http://polymer.hnu.kr/sub/sub02/sub_0201.jsp Gold-plated helices written with 3D laser lithography courtesy

• f Karlsruhe Institute of

Technology (KIT),

• J. Gansel et al.

http://www.cope.gatech.edu/rese arch/photoniccrystals.php

NANOTECHNOLOGY

µm- nm-

• ‘top-down’: lithography and printing

mature serial processes limited in sub-50 nm range

• ‘bottom-up’: self-assembly

molecular-level feature definition need of fundamental research new materials and functional systems

J.V. Barth et al. Nature, 2005, 437, 671

Approaches to Nanofabrication

‘Bottom-up’ Strategy

• Instead of taking material away to make structures,

the bottom-up approach selectively adds atoms/molecules to create structures.

J.V. Barth et al. Nature, 2005, 437, 671

D = diffusion rate F = deposition flux

When atoms/molecules are absorbed on substrate the type of growth is determined by the D/F ratio kinetic vs thermodynamic control in surface structuring

Diffusion limited regime Cu chains on Pd (110) Ag dendrites on Pt (111) Strain relaxation Ge SC Qdots on Si(100) BN nanomesh on Rh(111) Molecular self-assembly Benzoic acid based molecules @Ag (111) Scale bar = 20 nm

‘Bottom-up’ Strategy

• Molecular self-assembly at surfaces

1) Self-assembled monolayers (SAMs)

• SAMs provide a convenient, flexible, and simple system to tailor the interfacial properties of

metals, metal oxides, and semiconductors.

• SAMs are organic assemblies formed by the adsorption of molecular constituents from

solution or the gas phase onto the surface of solids

• The adsorbates organize spontaneously (and sometimes epitaxially) into crystalline (or

semicrystalline) structures.

• The molecules that form SAMs have a chemical functionality, or “headgroup”, with a specific

affinity for a substrate;

• The most extensively studied class of SAMs is derived from the adsorption of alkanethiols on

gold

‘Bottom-up’ Strategy

• Molecular self-assembly at surfaces

1) Self-assembled monolayers (SAMs)

George M. Whitesides et al. Chemical Reviews, 2005, Vol. 105, No.4

• SAMs are themselves nanostructures; the thickness of a SAM is typically 1-3 nm
• The composition of the molecular components of the SAM determines the atomic

composition of the SAM perpendicular to the surface; this characteristic makes it possible to use

• rganic synthesis to tailor organic and organometallic structures at the surface with positional control

approaching0 .1 nm.

• They are easy to prepare, they can couple the external environment to the electronic and
• ptical properties of metallic structures, they link molecular-level structures to macroscopic

interfacial phenomena, such as wetting,adhesion, and friction.

‘Bottom-up’ Strategy

• Molecular self-assembly at surfaces

1) Self-assembled monolayers (SAMs)

George M. Whitesides et al. Chemical Reviews, 2005, Vol. 105, No.4

• Drawback: No control of the lateral order

‘Bottom-up’ Strategy

• Molecular self-assembly at surfaces

2) Supramolecular Chemistry at Surfaces “Chemistry of Molecular Assemblies and of the Intermolecular non- covalent Bond.” “Chemistry Beyond Molecule” Jean-Marie Lehn (Nobel prize, Chemistry, 1987) What is Supramolecular Chemistry ? DNA:

cooperative bonding Self-assembly

‘Bottom-up’ Strategy

Supramolecular chemistry focuses on the chemical systems made up of a discrete number of assembled molecular subunits or components.

• Molecular self-assembly at surfaces

2) Supramolecular Chemistry at Surfaces What is Supramolecular Chemistry ?

Qualitative comparison of the relevant length scales over which each type of force dominates the self-assembly.

Forces controlling fabrication of molecular materials

• P. Samori,
• Angew. Chem. Int. Ed. 2007, 46, 4428

Noncovalent synthesis: considerate use of weak intermolecular interactions to synthesize supermolecules with a high degree of structural complexity Tecton: derived from Greek τεκτων (builder), molecular building block programmed for the assembly of an architecture with specific spatial or functional features Molecular recognition: selective association of complementary functional molecular groups or a receptor and a guest species; Based on ‘lock-and-key’principle with carefully designed functional molecular building blocks, weak and selective noncovalent linkages program the formation of supramolecular architectures

‘Bottom-up’ Strategy

Hierarchical self-assembly

H-bonds in Nature

• Oligo(p-phenylenevinylene)s with pendant diamino triazine moieties can self-assemble

through hydrogen-bonding interactions to give hexameric rosettes.

‘Bottom-up’ Strategy

π-Conjugated Oligo-(p-phenylenevinylene) Rosettes and their Tubular Self-Assembly

Representation of clockwise (CW) and counterclockwise (CCW) rosette structures showing the respective hydrogen-bonding patterns

• These rosettes further organize into large supramolecular tubules.

H-bonding π- π interactions

• E. W. Meijer Angew. Chem. Int. Ed. 2004, 43, 74 –78

7 nm

OUTLINE 1 – How to Shape Matter Macro vs Nanoworld 2 – Supramolecular chemistry at Surfaces Supramolecular chemistry Supramolecular chemistry at surfaces STM 3 – 2D Supramolecular Self-Assembly Hydrogen bond interaction Metal ligand interaction Van der Walls interaction 4- Our Contribution From Molecular ‘Clip’ to 3D Janus Tecton

* Noncovalent synthesis in two dimensions: 2D Supramolecular chemistry Mo Mole lecu cule le- Surfa face interactions

Ad Adsor

• rpti

tion

• n (Ead)

Therma mal migr grati tion

• n (Em)

Rota

• tati

tion

• nal moti
• tion
• n (Erot
• t)

Mo Mole lecu cule le- Mo Mole lecu cule le lateral interactions

Non

• n- cova
• valent bo

bond nd for

• rmati

tion

• n (Eas)
• Hydrogen bonding
• Metal-ligand interactions
• Van der Waals interactions

Engineering Nanostructures on Surfaces

Erot Ead Em Eas

* Applications:

• Molecular machines,
• Nano-bio interface
• Nanoelectronics,
• Nanophotonics…

Engineering Nanostructures on Surfaces

tectons

shape & symmetry functional groups concentration

balanced interactions

substrate

atomic structure chemical nature nano-templates

self-assembled architectures

STM Imaging of Atomic Structure Scanning Tunneling Microscopy

Gerd Binnig Heinrich Rohrer

Nobel Price in Physics 1986 In scanning tunneling microscopy a bias voltage is applied between a sharp metal tip and a sample. When the tip approaches very closely to the sample, a tunnel current can flow from sample to tip (or vice versa depending on the polarity of the bias voltage). This tunneling phenomena can be described by quantum mechanics. If the tunnel current is kept constant using a feedback loop, the surface morphology can be scanned with the tip. By monitoring the vertical z position during the scan, we can

• btain a topographical image of the

sample surface.

I ∞ e-z/z0

STM Imaging of Atomic Structure

• Tip (Au, Pt,…)
• Substrate Au(111), HOPG
• Tunnel current (~pA)
• STM Junction
• usually under ultrahigh-vacuum (UHV) conditions
• The governing principle of scanning tunneling microscopy (STM) is the quantum tunneling of

electrons through a thin potential barrier separating two electrodes.

Atomic-scale resolution images of surfaces (density of electronic states) Au (111) reconstruction

Scanning Tunneling Microscopy

• Tip (Au, Pt,…)
• Substrate Au(111), HOPG
• Tunnel current (~pA)
• Liquid (nC14H30)
• STM Junction
• Immersed in a liquid

>Low conductivity

>Hydrophobic (non polar)

STM at the Liquid / Solid Interface

>Tunnel and transfer medium

• Tip (Au, Pt,…)
• Substrate Au(111), HOPG
• Tunnel current (~pA)
• Liquid (nC14H30)
• Solvated molecules
• STM Junction
• Immersed in a liquid / solution

STM at the Liquid / Solid Interface

• Tip (Au, Pt,…)
• Substrate Au(111), HOPG
• Tunnel current (~pA)
• Liquid (nC14H30)
• Solvated molecules
• Self-assembled monolayer
• STM Junction
• Immersed in a solution
• Self-assembled monolayers

STM at the Liquid / Solid Interface

Atomic-scale resolution images of surfaces (density of electronic states) Team of F. Charra, CEA , France

OUTLINE 1 – How to Shape Matter Macro vs Nanoworld 2 – Supramolecular chemistry at Surfaces Supramolecular chemistry Supramolecular chemistry at surfaces STM 3 – 2D Supramolecular Self-Assembly Hydrogen bond interaction Metal ligand interaction Van der Walls interaction 4- Our Contribution From Molecular ‘Clip’ to 3D Janus Tecton

Self-Assembly of Monomolecular Systems: Bidentate building blocks

2D Supramolecular self-assembly: hydrogen bond interaction

‘‘zigzag’’ pattern

• Assembly of isophthalic acid at solid/liquid interface leads to

zigzag chains Solvent induced polymorphism.

• S. Lei,S. De Feyter et al. Nano Lett., 2008, 8, 2541.

Self-Assembly of Monomolecular Systems: Tridentate building blocks

2D Supramolecular self-assembly: hydrogen bond interaction

STM topographs and corresponding models of two hexagonal TMA monolayer polymorphs on graphite: (a, b) chickenwire structure and (c, d) flower structure. in heptanoic acid in pentanoic acid

• 2D cross-linked networks
• Solvent induced polymorphism.
• M. Lackinger, and W. M. Heck, Langmuir 2009,

25(19), 11307–11321 l

Self-Assembly of Monomolecular Systems: Tridentate building blocks

2D Supramolecular self-assembly: hydrogen bond interaction

• Rigid spacers introduced between the central benzene core and the

peripheral carboxylic linker groups

• 2D nanoporous networks with tunable cavity diameters

2.8 nm 1.7 nm 3.5 nm a) b) c)

Multicomponent: - angular unit: control of the shape

• linear unit: control of the size

Self-Assembly of Multimolecular Systems:

2D Supramolecular self-assembly: hydrogen bond interaction

Chemical structure of PTCDI (a) and melamine (b) Schematic diagram of a PTCDI–melamine junction

Peter H. Beton Nature 424, 1029-103,2003

STM image

• f

a PTCDI– melamine network Schematic diagram showing the registry of the network with the surface

Self-Assembly of Monoligand Systems

2D Supramolecular self-assembly: metal ligand interaction

Rectangular Fe-terephtalate array on Cu(100) with 1,4-benzenedicarboxylic acid (TPA) tectons and the carboxylate- bridged di-iron center coupling motif

• verlaid.

Lingenfelder M, N. Lin, J. V. Barth, K. Kern et al. 2004. Chem. Eur. J. 10:1913–19

• Fabrication of distinct Fe-carboxylate coordination architectures at the

surface by carefully adjusting the ligand and metal concentration ratio

• Fabrication of nanogrids

2D Supramolecular self-assembly: metal ligand interaction

b)–d) Arrays formed with increasing the length of the

• ligophenylene organic linkers.

Self-Assembly of Monoligand Systems

Ruben M, Barth JV, et al. Nanoletters, 7,2006.

Metal-organic nanomesh formed by Co-directed assembly of NC-Phx-CN linkers on Ag(111)

Giant Cavities

Ruben M, Barth JV, et al.

• J. Am. Chem. Soc. 2009, 131, 3881–3883.

• STM images show six possible binary combinations of

bipyridine (ligands 1a and 1b) and bis-carboxylic acid (ligands 2a, 2b, and 2c) ligands. All images are 9.4 6.0 nm. Structure periodicity is 1.1 1.8 nm (a), 1.5 1.8 nm (b), 1.8 1.8 nm (c), 1.1 2.3 nm (d), 1.5 2.3 nm (e), and 1.8 2.3 nm (f ).

• Steering the size and aspect ratio of rectangular molecular scale

compartments via the backbone length of the ligands in self-assembled iron coordination networks.

2D Supramolecular self-assembly: metal ligand interaction

Self-Assembly of Multiligand Systems

• S. L. Tait, M. Ruben, PNAS, 2007,

104, 17927–17930

2D Supramolecular self-assembly:van der Waals interactions

• Interdigitation of alkyl chains is a frequently encountered stabilization

motif within self-assembled monolayers of organic molecules, particularly at liquid–solid interfaces.

• This stabilization occurs not only by means of interactions between the

chains in a lattice, but also by van der Waals interactions with the surface running parallel to them.

• Graphite surfaces in particular have a high affinity for alkyl chains,

because of the high degree of structural matching, and the molecule– substrate interactions can generally be controlled by varying the chain length.

C30H62 Adsorption of n-Alkanes on HOPG

Cyr et al.

• Chem. Mat. 1996

2.46 Å

• 2. 51 Å
• Close match between intra-chain

periodicity and graphite lattice parameter.

• Good match between inter-chain

distance and graphite lattice parameter

4.6 Å

Highly stable ordered 2D layer (2D close-packing lamellae) High adsorption energy High 2D crystallization energy

Watel et al.

• Surf. Sci. 1993

STM image of C30H62 Schematic diagram of n-alkanes adsorbed on a hexagonal graphite substrate

Organization driven by two factors

~0.13eV/CH2

Packing ~0.025eV/CH2

2D Supramolecular self-assembly:van der Waals interactions

2D Supramolecular self-assembly:van der Waals interactions

Dehydroxybenzo[12]annulene

STM image of monolayer of 1 (b) & of 2. (19x19 nm2)

• Tentative packing models of 1 and 2

are superimposed in (a) and (b), respectively.

• The red lines highlight the network

symmetry, which is Kagome´ type for 1 and honeycomb type for 2. Schematic representation of the dense packing of ideal rhombic plates (left) and triangular plates (right) on a surface

• S. De Feyter et al.,

JACS, 128, 3502 (2006)

2D Supramolecular self-assembly:van der Waals interactions

Effect of alkyl chain length.

a) Molecular structure of annulenes. b) Alkyl chain length dependency of the 2D networks formed.

• S. De Feyter et al.,
• Angew. Chem. Int. Ed, 46, 2831 (2007)

2D Supramolecular self-assembly:van der Waals interactions

Effect of solute concentration.

• S. De Feyter et al.,
• Angew. Chem. Int. Ed, 3006 (2008)

Low concentration favor the honeycomb polymorph

2D Supramolecular self-assembly:van der Waals interactions

Guest-induced transformation.

• S. De Feyter et al.,
• Angew. Chem. Int. Ed, 46, 2831 (2007)

The addition of guest molecules to a linear nonporous two-dimensional network results in its transformation into a honeycomb porous network. The transformation shows guest selectivity

• A. J. Attias et al.,
• Angew. Chem. Int. Ed, 46, (2007)

Programmable Hierarchical Multi-Component 2D Assembly at a Liquid-Solid Interface: Recognition, Selection, and Transformation

• J. Adisoejoso, K. Tahara, S. Okuhata, S. Lei, Y. Tobe, S. De Feyter, Ang. Chem. Int. Ed., 2009, 48, 7353
• S. Lei, M. Surin, K. Tahara, J. Adisoejoso, R. Lazzaroni, Y. Tobe, S. De Feyter, Nano Lett., 2008, 8, 2541

2D Supramolecular self-assembly:van der Waals interactions

OUTLINE 1 – How to Shape Matter Macro vs Nanoworld 2 – Supramolecular chemistry at Surfaces Supramolecular chemistry Supramolecular chemistry at surfaces STM 3 – 2D Supramolecular Self-Assembly Hydrogen bond interaction Metal ligand interaction Van der Walls interaction 4- Our Contribution From Molecular ‘Clip’ to 3D Janus Tecton

OUTLINE 1 – Introduction – Context 2 – 2D Self-Assembly Tuning. Mole

• lecula

cular ‘Clip’ 3 – Janus-Like 3D π-Conjugated Tectons

Université Pierre et Marie Curie Paris 6

STM

JANUS PATER by Yuri Firsanov

STM

Molecular 'Clip' as a Tool for Two-Dimensional Self-Assembly on Surfaces: from Concept to 3D pi-Conjugated Janus Tectons towards Applications in Nanoscience

1 – Introduction – Context 2 – 2D Self-Assembly Tuning. Design of Molecular ‘Clip’ 3 – Janus-Like 3D π-Conjugated Tectons

2D Self-Assembly on HOPG

• CONTEXT:

Self-assembly at the Liquid-Solid Interface

• M. Lackinger et al.

Langmuir, 2005, 21, 4984

• K. Tahara et al.
• J. Am. Chem. Soc., 2006, 128, 16613
• S. Stephano et al.,
• Ang. Chem. Int. Ed., 2007, 46, 710

Planar π-conjugated building blocks

Multifunctional nanodevices:

• achieving nanometer-scale control over the positioning and
• rganization of molecules into monolayers at surfaces

bottom-up approaches supramolecular chemistry Hydrogen Bonds Coordination Van der Waals Interactions

Ag(111), UHV HOPG, Liq Sol Interf HOPG, Liq Sol Interf

‘Chickenwire Structure’ ‘Flower structure’

• M. Lackinger et al. Langmuir, 2005, 21, 4984
• K. Tahara et al. J. Am. Chem. Soc., 2006, 128, 16613

No topological relationship with the substrate Minute changes in molecular structure or solvent may induce drastic structural changes of the self-assembled patterns in unpredictable ways

2D Self-Assembly on HOPG

Topologies (and structural changes) usually explained a posteriori Multifunctional nanodevices:

• achieving nanometer-scale control over the positioning and
• rganization of molecules

bottom-up approaches supramolecular chemistry Hydrogen Bonds Van der Waals Interactions

• CONTEXT:

Self-assembly at the Liquid-Solid Interface

• OBJECTIVES:

Steered self-assembly at the Liquid-Solid Interface

• OUR STRATEGY:

Design of a new molecular unit to access an atomically-precise 2D organization

• Molecule-substrate epitaxial adsorption
• Intermolecular bonding

« mole lecu cula lar cli clip »

• exact placement of each molecule over the substrate
• specific topologies ‘on
• n de

dema mand’’

2D Self-Assembly on HOPG

Citation #: ~ 55 ; D. Bléger, A. J. Attias et al. Angew. Chem. Int. Ed. 46(39), 2007, 7404

1 – Introduction – Context 2 – 2D Self-Assembly Tuning. Design of Molecular ‘Clip’ 3 – Janus-Like 3D π-Conjugated Tectons

2D Self-Assembly on HOPG: ‘CLIP’ Concept ‘MATRIX’ EPITAXIAL STRUCTURE

H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

• Molecule-substrate bonding:

adsorption in registry with HOPG

• Molecule-molecule bonding:

packing stabilization (“clips”)

H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

a a

Formation of Molecular « Clip »

a = 0.43 nm 2a a

• D. Bléger, A. J. Attias et al. Angew. Chem. Int. Ed. 46(39), 2007, 7404

⇒Surface-induced non-covalent bonds close-packing structure

2D Self-Assembly on HOPG: ‘CLIP’ Concept Validation Parallelism with polymer chemistry !

• D. Bléger, A.-J. Attias et al. Angew. Chem. Int. Ed. 46(39), 7404, (2007)

1 clip 2 clips 3 clips

• G. Schull, A. J. Attias et al. Nano Letters, 6, (2006)

Dimers Linear polymeric chains Honeycomb 2D network

8.0 x 8.0 nm

Quantitative Proofs: Epitaxial Relationship

alkyl chains along a symmetry axis <100>HOPG ⇒ 2 types of domains (enantiomers) ⇒ by symmetry, angles of +/-θ with <100>HOPG

θ i

H H H H H H H H H H H H H H

HOPG network Honeycomb network (one domain)

O O O O O O

a

163 163×

R 11.7° ∅=0.7nm

φ

• C6H13

<100>HOPG

i = 2.44Å aexp= 12.77Å ath= 12.5Å

Good agreement between experimental and theorical results

Epitaxial Relationship & Controlled Tuning of Pore Size

Description of the molecule-substrat registry

• C. Arrigoni , A. J. Attias et al. J. Phys. Chem. Lett, 2010

8.0 x 8.0 nm

2D Self-Assembly on HOPG: ‘CLIP’ Concept Generalization !

O O O O

N N

O O O O

• D. Bléger, A. J. Attias et al. Angew. Chem. Int. Ed. 46(39), 2007, 7404

• D. Bléger, A. J. Attias et al. Angew. Chem. Int. Ed. 46, 2007

2D Self-Assembly on HOPG: ‘CLIP’ Concept

• C. Arrigoni, A. J. Attias et al. J. Phys. Chem. Lett, 2010

Au (111)

87×57 nm2

Versatility of Clip Concept

Submitted

• Liquid (nC14H30)
• Solvated molecules
• Self-assembled

HOST monolayer

• GUEST molecules

Nanoporous Host-Guest Networks:Dynamic Properties

• guest-induced transformation
• f molecular networks
• guest co-adsorption

in porous network

2D Self-Assembly: Higher Organization Level Surface coverage completed uncompleted

More compact Uncovered void Linear polymeric chain Cyclic hexamer (oligomer)

O O O O

clip 1

2D Self-Assembly: Higher Organization Level

+ + 60°C

Hexabenzocoronene

26.0 x 19.0 nm

HIERARCHICAL ORGANIZATION

• D. Bléger et al. Angew. Chem. Int. Ed. 46(39), 2007, 7404

DIABOLI LICA CAL TRAP! P!

2D Self-Assembly: Higher Organization Level

26.0 x 19.0 nm

+

60°C

Hexabenzocoronene

• D. Bléger, A.-J. Attias et al. Angew. Chem. Int. Ed. 46(39), 2007, 7404

HIERARCHICAL ORGANIZATION « template effect »

DIABOLI LICA CAL TRAP! P!

• Nanoporous matrix
• Three parts :

– Conjugated core – Densely-packed aliphatic chains (epitaxial assembly & interdigitation) – Empty pore (∅ = 1.3 nm)

O O O O O O

Honeycomb structure 2D Nanoporous Network: Molecular Sieve?

2D Nanoporous Network: Molecular Sieve?

Free-substrate cavities are selective adsorption zones for guest molecules.

Honeycomb structure 2D Molecular Sieve

Honeycomb structure 2D Nanoporous Network: Dynamic Aspect 2D Molecular Sieve

Addition of Sub-stoichiometric guest solutions

Guest: Hexabenzocoronene

• partially-filled matrix,
• nearly-random distribution of
• ccupied pores,
• No change in distribution of

HBC for > 10 min.

Honeycomb structure 2D Nanoporous Network: Dynamic Aspect

Thermally activated pore-to-pore hopping

• f guest molecules

Citation #: ~80 ; G. Schull, A.-J. Attias et al. Nano Letters, 6, 2006

2D Molecular Sieve

(kT)-1 [(eV)]-1 Ln(1/ τ) [ ln s-1] 38 40 42 44

• 2

2 4

35°C : 40ms

• 9°C : 5s

Addition of Sub-stoichiometric guest solutions

Guest: Coronene

Honeycomb structure 2D Nanoporous Network: Dynamic Aspect

Thermally activated pore-to-pore hopping

• f guest molecules
• G. Schull et al. Adv Mater, 18, 2006

Selectivity on guest size and shape Fine tuning of matrix selectivity

2D Molecular Sieve

Different host matrices, Same guest molecules

INFLUENCE OF ALKYL CHAIN-LENGTH

Honeycomb structure 2D Nanoporous Network: Dynamic Aspect

Thermally activated pore-to-pore hopping

• f guest molecules
• G. Schull, A.-J. Attias et al. Adv Mater, 18, 2006

Selectivity on guest size and shape Fine tuning of matrix selectivity

2D Molecular Sieve

Same host matrix, Different guest molecules Different host matrices, Same guest molecules

Citation #: ~80 ; G. Schull, A.-J. Attias et al. Nano Letters, 6, 2006

Dynamic ic P Pro rope pert rtie ies

• Angew. Chem. Int. Ed. 46, 2007

From 2D to 3D Architectures

• Features: in

in- plane ne c confi nfine ned Forthcoming applications require

Honeycomb structure

Thermally activated pore-to-pore hopping

• f guest molecules

Adv Mater, 18, 2006

2D Molecular Sieves

Nano Letters, 6, 2006

• J. Phys. Chem. C, 2008
• J. Chem. Phys., 134, 2011
• Angew. Chem. Int. Ed. 46, 2007

Diabolical Trap

• J. Phys. Chem. Lett, 2010

To create

• ut-of-plane functions

To fully exploit the room above the substrate

Dynamic ic P Pro rope pert rtie ies

• Angew. Chem. Int. Ed. 46, 2007

From 2D to 3D Architectures

• Accurate 2D positioning:

mastered Controlled placement

• f objects

in the third dimension may be envisaged

Honeycomb structure

Thermally activated pore-to-pore hopping

• f guest molecules

2D Molecular Sieves

• Angew. Chem. Int. Ed. 46, 2007

Diabolical Trap

• J. Phys. Chem. Lett, 2010

Adv Mater, 18, 2006 Nano Letters, 6, 2006

• J. Phys. Chem. C, 2008
• J. Chem. Phys. , 134, 2011

Dynamic ic P Pro rope pert rtie ies

• Angew. Chem. Int. Ed. 46, 2007
• Angew. Chem. Int. Ed. 47, 2008

From 2D to 3D Architectures

3D 3D Fun unctio ional Buil Buildin ing Bl Blocks

Honeycomb structure

Thermally activated pore-to-pore hopping

• f guest molecules

2D Molecular Sieves

• Angew. Chem. Int. Ed. 46, 2007

Diabolical Trap

• J. Phys. Chem. Lett, 2010

Adv Mater, 18, 2006 Nano Letters, 6, 2006

• J. Phys. Chem. C, 2008
• J. Chem. Phys., 134, 2011
• Angew. Chem. Int. Ed. 50, 2011

Towards Nanophotonics/Electronics: The Issues

On metallic surface: quenching

Isolated Close to the substrate

Broadening and lowering of

• rbitals by

coupling

X.H. Qiu, G.V. Nazin, and W. Ho, Science, 299 , 542-546 (2003).

• M. J. Comstock, N. Levy, A. Kirakosian, J. W.

Cho, F. Lauterwasser, J. H. Harvey, D. A. Strubbe, J. M. J. Fréchet, D. Trauner, S. G. Louie and M. F. Crommie. Physical Review Letters, 99, 038301 (2007)

• J. Repp, G. Meyer, S. M. Stojkovic,
• A. Gourdon, C. Joachim,
• Phys. Rev. Lett.. 94, 026803 (2005)
• M. Yu, N. Kalashnyk, W. Xu, R. Barattin,
• Y. Benjalal, E. Laegsgaard,
• I. Stensgaard, M. Hliwa, X. Bouju, A. Gourdon,
• C. Joachim, F. Besenbacher, T. R. Linderoth,

ACS Nano, 4, 4097-4109 (2010)

Towards Nanophotonics: The Issues Limited to short-range organization.

• Measurements

in a UHV-STM tip-molecule-metallic surface experiment,

• Sometimes at low temperature.

PREVIOUS APPROACHES: Designing tectons able to combine the following functions:

• se

self- asse ssembling wi with long- range la late tera ral order

• exp

xpos

• sing the

the des esired ed fun unctio ion de deco couple pled fr from a co condu nducti cting ng su subst strate OUR APPROACHE:

1 – Introduction – Context 2 – Self-Assembly Tuning. Design of Molecular ‘Clip’ 3 – Janus-Like 3D π-Conjugated Tectons Why and nd How

• w to

to Rea Reach th the 3rd

rd Di

Dime mensi sion?

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons OUR STRATEGY:

• Taking advantage of the control of the 2D self-assembly

to reach the 3rd Dimension

JANUS (two wo- fa faced) ) 3D B 3D Buil uildin ing- Blo Block ck

• n
• ne face

ce is is a fu func nctiona nal mole lecu cule le

• n
• ne face

ce is is de desi signed for

• r steerin

ring 2D se self- asse ssemb mbly

JANUS PATER by Yuri Firsanov

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons

rig rigid id pil pillar r as l lin inke ker

JANUS (two wo- fa faced) ) 3D B 3D Buil uildin ing- Blo Block ck

• n
• ne face

ce is is a fu func nctiona nal mole lecu cule le

• n
• ne face

ce is is de desi signed for

• r steerin

ring 2D se self- asse ssemb mbly

OUR STRATEGY:

• Taking advantage of the control of the 2D self-assembly

to reach the 3rd Dimension

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons OUR STRATEGY:

• Taking advantage of the control of the 2D self-assembly

to reach the 3rd Dimension Tunable height Pillar Tunable height Pillar rig rigid id pil pillar r as l lin inke ker

JANUS (two wo- fa faced) ) 3D B 3D Buil uildin ing- Blo Block ck

• n
• ne face

ce is is a fu func nctiona nal mole lecu cule le

• n
• ne face

ce is is de desi signed for

• r steerin

ring 2D se self- asse ssemb mbly

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons

• emergence of a periodic array of nanopillars

pe perpe rpendic icul ular to th to the su subst strate

control the positioning of out-of plane functional unit

• well-organized in-plane monolayer paving the substrate

Precise organization of chromophores arrays a few Å above the conducting surface. OUR STRATEGY:

• Taking advantage of the control of the 2D self-assembly

to reach the 3rd Dimension dual-functionalized unit

Janus (two faced) building block

• Solvated molecules
• Self-assembled monolayer

Substrate

1 – Introduction – Context 2 – Self-Assembly Tuning. Design of Molecular ‘Clip’ 3 – Janus-Like 3D π-Conjugated Tectons Why and nd How

• w to

to Rea Reach th the 3rd

rd Di

Dime mensi sion?

Designing tectons able to simultaneously  se self- asse ssemble wi with long- range la late tera ral order

• exp

xpos

• se the

the des esired ed fun unctio ion de deco couple pled fr from a co condu nducti cting ng su subst strate

JANUS (two wo- fa faced) ) 3D B 3D Buil uildin ing- Blo Block ck

• n
• ne face

ce is is a fu func nctiona nal mole lecu cule le

• n
• ne face

ce is is de desi signed for

• r steerin

ring 2D se self- asse ssemb mbly

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons OUR STRATEGY:

• Taking advantage of the control of the 2D self-assembly

to reach the 3rd Dimension Tunable height Pillar Tunable height Pillar

‘2-layered’ molecule

C10H21O C10H21O OC10H21 OC10H21 C10H21O C10H21O OC10H21 OC10H21 C10H21O C10H21O OC10H21 OC10H21

‘3-layered’ molecule

= ≈3,0 Å ≈6,0 Å

• D. Bléger, A.-J. Attias et al. Angew. Chem. Int. Ed. (2008)

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons Validation (1)

Paracyclophane

Alkyl chains Pedestal Column

20 x 20nm2 ; It = 71pA

0,0 1,0 2,0 2 4 6 8 10 nm Å

• App. height

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons

~ 3.86 nm

cyclophanes DO NOT disturb the assembly in linear chains (even at large scales) → rigid up-standing (face-on) nanopillars paving HOPG with long-range ordering

Validation (1)

0,0 1,0 2,0 2 4 6 8 10 nm Å

• App. height

~ 3.86 nm

Molecular scheme of one unit cell

Epitaxial relationship

a = 3.84 nm, b = 2.08 nm, α = 63.9° θ = 10°

cyclophanes DO NOT disturb the assembly in linear chains (even at large scales) → rigid up-standing (face-on) nanopillars paving HOPG with long-range ordering

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons

Active component

Top View

S S MeO2C CO2Me Br Br HS SH Br Br

a) KOH

CO2Me MeO2CBr Br

c) DIBAL-H e) Pd(PPh3)4

C10H21O C10H21O PO(OEt)2 +

2 3 4

6: R = CO2Me 7: R = CHO 8 d) PCC

B OMe MeO

b)

O O 5

tBuOK

R R S S MeO MeO OMe OMe

« clip » triphenylenevinylene

≈3,3 Å

Triphenylenevinylene

Validation (2)

• D. Bléger, A.-J. Attias et al. Angew. Chem. Int. Ed. (2011)

« clip »

triphenylenevinylene

2D Self-Assembly: Janus-Like 3D π-Conjugated Tectons

• The ‘floor’ doesn’t disturb the self-assembly in linear chains

(even at large scales)

• Multistory molecules build-up perpendicular to the substrate

(paving HOPG with long-range ordering)

100nmx100nm

Validation (2)

Control of the positioning and organization

• f potential subwavelength emitters….

50nmx50nm

X

De Desi sign o

• f Functi

tion

• nal Buil

Buildin ing Bl Blocks ks Active center

Fluorescent

C10H21O C10H21O R S S S S R OC10H21 OC10H21 n n

A

n = 0, 1, 2 or 3

“Clip” Tuning of emission

Janus-Like 3D π-Conjugated Tectons based on Nanowires

De Desi sign o

• f Functi

tion

• nal Buil

Buildin ing Bl Blocks ks Active center

Fluorescent n = 0, 1, 2 or 3

Tuning of electronical properties

Janus-Like 3D π-Conjugated Tectons based on Nanowires

300 400 500 600 0,0 0,2 0,4 0,6 0,8 1,0 Normalized Intensity (a.u) wavelength (nm)

S S S S S S C8H17 C8H17 S C8H17 S S S C8H17 C8H17 S S C8H17

Absorption Emission

Upper decks

De Desi sign o

• f Functi

tion

• nal Buil

Buildin ing Bl Blocks ks Active center

Fluorescent

O O O O Br Br S R S S B O O n +

• 1. Suzuki
• 2. H+

OHC S S S S R R CHO n n C10H21O C10H21O PO(OEt)2 C10H21O C10H21O R S S S S R OC10H21 OC10H21

n n

Wittig-Horner n = 0,1,2,3 n = 0,1,2,3 Final Foundry Derived Target From UPMC Chemical Library Final UPMC Derived Target C D A E

Janus-Like 3D π-Conjugated Tectons based on Nanowires

CONCLUSIONS

• Toolbox for rational design of

steered self-assembled monolayers on HOPG.

• Combination, at the nanoscale, of in

in- plane and of

• ff- pla

plane

• rganization:

exact positioning of vertical structural elements. Promising route to insert 3D functional nanostructures into 2D lattices

• Versatility of the building block design.

Active center

Fluorescent, Photoswitchable Nanowires Redox, Magnetic properties…..

Substrate: Graphene, Au

• Observation of emission (in progress)

ACKNOWLEDGEMENTS

Laboratoire de Chimie des Polymères, Université Paris 6

• Drs. David Bléger, Claire Arrigoni , Imad Arfaoui

Amina Bakhma (Ph. D Student) Amandine Bocheux (Ph. D Student) Antoine Colas (Ph. D Student)

• Dr. Ping Du (Post-doc)
• Dr. Elena Zaborova (Post-doc)
• Dr. David Kreher (Assistant Professor)
• Dr. Fabrice Mathevet (Researcher-CNRS)

Synthesis

DSM-DRECAM, CEA

• Dr. Guillaume Schull

Amandine Bocheux (Ph. D Student)

• Dr. Fabrice Charra
• Dr. Ludovic Douillard
• Dr. Céline Fiorini-Debuisschert

STM

Berkeley Lab. – USA

• Dr. Brett Helms

Funding agencies

감사합니다 !

Thank you for your attention!