Molecular chirality at surfaces

A.L. Vázquez de Parga, UAM

Chirality timeline

Archimedes of Syracuse (250 BC), Dominique F.J. Arago (1811), Jean-Baptiste Biot (1835),
the design of the Archimedean discovery of the rotation of discovery of the rotation of
water screw and the study of the the polarization of light in the polarization of light in
spiral structure quartz crystals sugar solution

A.L. Vázquez de Parga, UAM

What chirality means?

“I call any geometrical figure, or group of points, chiral, and say it has chirality if its
image in a plane mirror, ideally realized, cannot be brought to coincide with itself”

Lord Kelvin (1893)

The word chirality comes from

the greek word cheir, that
means hand

A.L. Vázquez de Parga, UAM

What chirality means?

Chiral objects Achiral objects

Hands Pencil

Snails
A.L. Vázquez de Parga, UAM
What chirality means?
SPIRAL GALAXIES

M51 M83
The Whirlpool Nebula Southern Pinwheel

A.L. Vázquez de Parga, UAM

What chirality means?

no inversion symmetry elements

CANNOT BE SUPERIMPOSED

A geometrical property with profound implications for

PHYSICS CHEMISTRY BIOLOGY

A.L. Vázquez de Parga, UAM

What chirality means?
The tetrahedral carbon
Van’t Hoff & Le Bel 1874.

A.L. Vázquez de Parga, UAM

What chirality means?

The tetrahedral carbon Stereochemistry/Molecular chirality
Van’t Hoff & Le Bel 1874. Fischer 1894/ Prelog 1975

C C

Optical isomers enantiomers chiral molecules

A mixture consisting of equal parts of any pair of enantiomers is called a

racemic mixture

A.L. Vázquez de Parga, UAM

What chirality means?

A.L. Vázquez de Parga, UAM

Chirality
Enantiomers can be identified using the letters D and L or R and S in front of the name
of the molecule

Optical isomers: substances which appeared to be identical chemically and physically,

except that one form rotated the plane of polarised light to the right (D from latin dexter)
and another to the left (L from latin laevus).
(R) & (S) configuration:
1. -Identify the chirality centers (usually an sp3 C with 4 different groups attached)
2. -Assign the priority to each group (high = 1, low = 4) based on atomic number of the
atom attached to the chirality center (remember the first point of difference rule)
3. -Position the lowest priority group away from you
4. -For the other 3 groups, determine the direction of high to low priority (1 to 3)
5. -If this is clockwise, then the center is R (Latin: rectus = right)
6. -If this is counter clockwise, then it is S (Latin: sinister = left)

A.L. Vázquez de Parga, UAM

Why chirality is important?
HOMOCHIRALITY OF LIFE ON EARTH

CH3
H
C S-alanine
H2N COOH
α-helix
Natural amino-acids (Pauling 1950)

CH3
H
R-alanine
C
COOH H2N

A.L. Vázquez de Parga, UAM

Why chirality is important?

Most drugs consist of chiral molecules. And since a drug must match the molecules it
should bind to itself in the cells, it is often only one of the enantiomers that is of
interest. In certain cases the other form may even be harmful.

(R)-limonene smells of oranges while its enantiomer (S)-limonene smells of lemons

A.L. Vázquez de Parga, UAM

Why chirality is important?

D-thalidomide: relieved morning L-thalidomide: mutagenic

sickness in pregnancy agent, teratogen

S-limonen: odor of lemon R-limonen: odor of orange

S-penicillamine: antiarthritic drug R-penicillamine: highly toxic

S-propanolol: beta- blocker R-propanolol: active

(heart disease) contraceptive

Some examples of profoundly different responses

exhibited by the human body to opposite enantiomers.

A.L. Vázquez de Parga, UAM

Asymmetric synthesis

It is very important for the industry to be able to produce products as pure as possible

Y H Y Z Y H
Z
+
H H Z
X X X

Y
Y Y O
-
Z Z
O +
X - Z
O X
X

When the molecules are produced in the laboratory under normal conditions the
synthesis is symmetric

A.L. Vázquez de Parga, UAM

Asymmetric synthesis

Nobel Prize in Chemistry 2001 was awarded to W.S. Knowles, R. Noyori and K.B.
Sharpless for their development of catalytic asymmetric synthesis

The hands on the right symbolise the catalyst and the hands on the left the product

A.L. Vázquez de Parga, UAM

Chiral catalysis at solids Chiral modifier

Chirally modified solid surfaces

Reactant

Attaching chiral auxillaries to reactant

or as support
for active centres
‘bare’
Intrinsically chiral solid or surface

A.L. Vázquez de Parga, UAM

Chiral catalysis at solids
sp2-prochiral centre

CH 2COOCH 3 CH 2COOCH 3
CH 2COOCH 3
H3C H3C
H3C
C C
C
H HO H
OH
O

(S)-MHB (R)-MHB
+2H+ +2H+
MAA

Metal Surface
e.g. nickel

MAA is Methylacetoacetate
R(S)-MHB are R(S)-Methyl-3-hydroxybutyrate

A.L. Vázquez de Parga, UAM

Chiral catalysis at solids

sp2-prochiral centre

CH 2COOCH 3
CH 2COOCH 3
H3C
H3C C
C
HO H
O

(R)-MHB
+2H+
MAA

R,R-TA/Metal
or
S-Alanine/Metal

MAA is Methylacetoacetate
R(S)-MHB are R(S)-Methyl-3-hydroxybutyrate
R,R-TA is R,R Tartaric acid

A.L. Vázquez de Parga, UAM

Chiral catalysis at solids
sp2-prochiral centre

CH 2COOCH 3
CH 2COOCH 3
H3C
H3C
C
C
H
OH
O

(S)-MHB
+2H+
MAA

S,S-TA/Metal
or
R-Alanine/Metal

MAA is Methylacetoacetate
R(S)-MHB are R(S)-Methyl-3-hydroxybutyrate
R,R-TA is R,R Tartaric acid

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?

An important question to answer is: do chiral molecules adsorb and self organise at
the metal surface?

Achiral (110) fcc surface Chiral molecule

NH2
CH3

O OH
[110]

S-alanine

[001]
R. Raval, University of Liverpool
A.L. Vázquez de Parga, UAM
How is chirality expressed at a surface?

Phase diagram for S-Alanine/Cu(110) LEED diagrams

H H

470K H

C
C
H

p1g1(3x2)
H

C
C
H

H H

C H C H
H H
N N
O O O O

420 localised
H
H
H

C
H

⎛ 5 3⎞
H H

H C
O

- ⎜⎜ ⎟⎟
H
H

ordering
H C C
C
H
H

⎝ − 2 2⎠
H N
C
C
H
C H
H

300K
N
O O
C H O
H
N
O O

H complex local H
H
H

C
H

& extended
H H

H C H C

80K
O
H
C
C C

order
H H H N H
C

C H C H
H H
N N
O O O O O

satn ML
increasing coverage

R. Raval, University of Liverpool

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?

p1g1(3x3) array created by S-Alanine on Cu(110) at 480K

LEED 48eV

[001] [001]

-
[110]
[110]

Pseudo-glide plane
p1g1(3x2) S-alanine structure on Cu{110}
STM image (100Å x 100Å)

R. Raval, University of Liverpool

A.L. Vázquez de Parga, UAM
How is chirality expressed at a surface?

Phase diagram for S-Alanine/Cu(110) LEED diagrams

H H

470K H

C
C
H

p1g1(3x2)
H

C
C
H

H H

C H C H
H H
N N
O O O O

420 localised
H
H
H

C
H

⎛ 5 3⎞
H H

H C
O

- ⎜⎜ ⎟⎟
H
H

ordering
H C C
C
H
H

⎝ − 2 2⎠
H N
C
C
H
C H
H

300K
N
O O
C H O
H
N
O O

H complex local H
H
H

C
H

& extended
H H

H C H C

80K
O
H
C
C C

order
H H H N H
C

C H C H
H H
N N
O O O O O

satn ML
increasing coverage

R. Raval, University of Liverpool

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?

CHIRAL 2-DIMENSIONAL ASSEMBLY

CHIRAL SURFACE
S-Alanine/Cu(110)

[001]

[110]

STM image (400Å x 400Å)

R. Raval, University of Liverpool

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?
Molecular Model of Chiral Surface

R. Raval, University of Liverpool

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?

Can surface chirality be switched?

S-Alanine R-Alanine

CH3 CH3

H H
C C
H2N H2N
COOH COOH

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?
S- and R- alanine self-organise to create “Extended Chiral Surfaces”

S-Alanine R-Alanine

STM image (150Å x 150Å) STM image (150Å x 150Å)

R. Raval, University of Liverpool Mirror

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?

2-Dimensional Chiral Switching

Schematic diagram of the S-alanine Schematic diagram of the R-alanine

structure on Cu(110) structure on Cu(110)
R. Raval, University of Liverpool
A.L. Vázquez de Parga, UAM
How is chirality expressed at a surface?

The benzoic acid is a two-dimensional

chiral species.

Homochiral molecules self-assemble

in supramolecular chiral hydrogen-
bonded twin chains

The molecule 4-[trans-2-(pyrid-4-yl-

vinyl)] benzoic acid (PVBA) is
deposited at RT on a noble metal
surface i.e. Ag(111), Au(111)

J. Weckesser et al, Phys. Rev. Lett. 87, 096101 (01)

A.L. Vázquez de Parga, UAM

How is chirality expressed at a surface?

A racemic mixture is deposited at the

surface, at RT the molecules undergo self-
assembly and only one supramolecular
chirality of the molecular twin chains exists
in domains extending micrometers
A.L. Vázquez de Parga, UAM
How is chirality expressed at a surface?

Deposition of additional PVBA at

160K. The new molecules
arrange into ramified structures
which area attached to the
existing twin chains

Upon gentle annealing to 225K, the molecular mass transport is limited to a short
range, and new metastable structures appear

Chirality
switches at
defects in new
twin chains

A.L. Vázquez de Parga, UAM