in silico approaches in metal organic frameworks: crystal...

In silico approaches in Metal organic Frameworks: Crystal structure prediction and computational design

of structure-property relationships

Caroline Mellot-Draznieks

Collège de France, 11 Place Marcelin Berthelot, Paris, 75005 Laboratoire de Chimie des Processus Biologiques, UMR CNRS-UPMC 8229

Rencontres Scientifiques de L’IFPEN, NEXTLAB 2014, Rueil-Malmaison, 2-4 Avril 2014

Outline

In the realm of Metal Organic Frameworks

1. Huge Structural diversity of Zeolitic Imidazolate Frameworks

Explore their energy landscape

Impact of the linker on the MOF’s energetics

2. Electronic properties of MOFs

Photocatalysis: Role of the organic linker in light capture

Computational screening experimental target

Outline



Tian et al. , Chem. Eur. J. , 2007, 13, 4146

Zeolites ZIFs

Si

Si

Si

Si Si

O

O

M

M

M

M M

145º 145.5º

Zeolitic IMIDAZOLATE FRAMEWORKS (ZIFs)

Yaghi et al. Nature Materials, 2007, 6, 501 and Acc. Chem. Res. 2010, 43 , 58.

> 16 linkers:

> 10 cations: Zn 2+, Li+, B3+, Mn2+, Fe2+, Co2+, Cu+, In2+, Cd 2+, Pr5+

moz SOD

GME

LTA

RHO poz

MER DFT ANA GIS


Yaghi et al. Nature Materials, 2007, 6, 501 and Acc. Chem. Res. 2010, 43 , 58.

moz SOD

GME

LTA

RHO poz

MER DFT ANA GIS

ZIFs versus zeolites Zeolites: 4-connected nets > 180 structure types ZIFs: 2,3,4,6-coordinated atoms ~ 30 structures types (including non-zeolitic types)

Diversity: ligand-directed strategies Substituted imidazolates Mixed linkers


ZIFs BIFs

Paucity of LiB-based ZiFs versus Zinc-based ZIFs BIF-1 (dia) BIF-2 (zni)

BIF-3 (SOD)

BIF-9 (RHO)

BIF-11 (SOD)

Role of substituents in linker-linker interactions?

Energy landscape of ZIFs:

Why are there so few LiB-ZIFs?

Which topology(ies) Which linker (s)?

Zn-based ZIFs LiB-based ZIFs

Unsubstituted linkers

Central role of dispersion interactions

without dispersion corrections

DFT-D PBE-D3

PBE-D2

PBE

stabilization of dense structures :

Galvelis, Slater, Cheetham, Mellot-Draznieks, CrystEngComm. 2012, 14, 374.

with dispersion corrections

zni

a = 23.503 Å3 b = 23.503 Å3 c = 12.461 Å3 V = 6883.1 Å3

a = 22.504 Å3 b = 22.504 Å3 c = 11.515 Å3 V = 5831.4 Å3

WITHOUT

DISPERSION

CORRECTION

Erro

r (%

)


a = 23.503 Å3 b = 23.503 Å3 c = 12.461 Å3 V = 6883.1 Å3

a = 22.504 Å3 b = 22.504 Å3 c = 11.515 Å3 V = 5831.4 Å3

(DFT-D)

WITH

DISPERSION

CORRECTION

A. K. Cheetham et al Chem.–Eur. J., 2010, 16, 10684.

Excellent bulk moduli predictions

Zn-zni 13.25 vs 14 GPa

LiB-zni 16.54 vs 16.6 GPa


Zinc- ZIFs

LiB- ZIFs

Galvelis, Slater, Cheetham, Mellot-Draznieks, CrystEngComm. 2012, 14, 374.

No difference between

Zn and LiB –ZIFs !!


Impact of the substituents in the energy landscape

7 topologies…

7 …crossed with 7 linkers


FAUJASITE- TYPE ZIF

BIF-3 BIF-9 BIF-11

We predict the Experimental stable

Structures !


Galvelis, Slater, Chaudret, Creton, Nieto-Draghi, Mellot-Draznieks, CrystEngComm. 2013, 15, 9603.

Possible structures?


Galvelis, Slater, Chaudret, Creton, Nieto-Draghi, Mellot-Draznieks, CrystEngComm. 2013, 15, 9603. BIF-3 BIF-9

= +

2 5 2,5



2.1 Å 1.5 Å

Different types of interactions

(arbitrary colour code)

H-bonds : < 0

van der Waals : ≈ 0

repulsion : > 0

E.R. Johnson et al, J. Am. Chem. Soc., 2010, 132, 6498-6506. J. Contreras-Garcìa, E.R. Johnson, S. Keinan, R. Chaudret et al, J .Chem. Theo. Comput., 2011, 7, 625-632.

Studying weak interactions with a NCI approach:

B-

Im

ImIm

Im

Li+

Li+

Im

Im

Li+

Li+

Im

Im

Intra interactions

Inter interactions

Studying weak interactions with a NCI approach:

NCI in SOD-type ZIFs

BIF-11

SOD


destabilizing

stabilizing

Linker –linker interactions in BIFs energy landscape

Subtle balance between repulsive interactions within Boron-

centred clusters (intra) and stabilizing ones between Boron-centred clusters (inter)

Versatility of the Li-Im bonds vs rigidity of the B-Im bond: the orientation of the linker is restricted

The position 4 maximize lateral linker-linker interactions, pointing towards the even larger impact of linkers with polarisable, charged or polar substituents (-NH2,-OH, -COOH, -NO2,-CH=O).

Outline



Explore their energy landscape

Impact of the linker on the MOF’s energetics

2. Electronic properties of MOFs

Photocatalysis: Role of the organic linker in light capture

Computational screening experimental target

MOFs and artificial photosynthesis

M M M M M

M M M

M M M

M M M

M M M

N N

Men+

N N

Men+

N N

Men+

N N

Men+

MOF as photosensitizer « semiconductor »

Organic linker used for anchoring the catalyst and chemical functionalization

Platforms for photoreduction of protons and CO2

CO2 CO Formate H2

M M M M M

M M M

M M M

M M M

M M M

N N

Men+

N N

Men+

N N

Men+

N N

Men+

CO2 CO Formate H2

W. Lin et al. J. Am. Chem. Soc. 2011, 133, 13445.


M M M M M

M M M

M M M

M M M

M M M

N N

Men+

N N

Men+

N N

Men+

N N

Men+

MOF as photosensitizer « semiconductor »

Organic linker used for anchoring the catalyst and chemical functionalization

Platforms for photoreduction of protons and CO2

CO2 CO Formate H2 Need to develop strategies to control the band gaps


M. Dan-Hardi, C. Serre, T. Frot, L. Rozes, G. Maurin, C. Sanchez, G. Férey, J. Am. Chem. Soc. 2009, 131, 10857.

[TiIV8O8(OH)4(O2C-C6H4-CO2)6] a = b = 18,654 Å c = 18,144 Å V = 6313,9 Å3

along [010] along [001]

Thermal stability up to 350°C

SBET = 1550 m²/g

MIL-125 : a Photoactive Porous Titanium(IV) Dicarboxylate

NH2

Y. Fu, D. Sun, Y. Chen, R. Huang, Z. Ding, X. Fu, Z. Li Angew. Chem. Int. Ed. 2012, 51, 3363-3367.

Amine-functionalized MIL-125 : a Photoactive MOF in visible light

3.6 eV/345 nm 2.6 eV/475 nm

Impact of mono-aminated linker

Computed band gaps of MIL-125 with functionalized linkers

MIL-125

MIL-125-bdc-NH2

CB

VB

MIL-125-NH2

NH2

Valence band

Conduction band

Hendon, Tiana, Fontecave, Sanchez, d’Arras, Sassoye, Rozes, Mellot-Draznieks, Walsh J. Am. Chem. Soc. 2013.

Impact of mono-aminated linker

Functionalizing the linker has a direct impact on the band gap

Computational screening of functional groups ?

MIL-125

MIL-125-bdc-NH2

CB

VB

MIL-125-NH2

NH2



∆BG = 1 ev

NH2

∆BG = 1.4 eV

NH2

NH2

Band

gap

(eV)

1

2

3

4

3.5

2.5

1.5

With an optical band gap of 1.3 eV, MIL-125-(NH2)2 is an excellent candidate


1.55 eV


DFT-D calculations (UCL) Dr. Raimondas Galvelis Dr. Ben Slater QSPR , NCI (IFPEn) Dr. Robin Chaudret Dr. Carlos Nieto-Draghi Dr. Benoit Creton Also A. K. Cheetham CNRS and EPSRC for financial support

DFT (Bath) Dr. Aron Walsh Chris Hendon Synthesis (Collège de

France) M. Fontecave C. Sanchez L. Rozes C. Sassoye

Acknowledgments

Seven topologies: SOD, RHO, DFT, GIS, MER, LTA and FAU. Seven methylated linkers Database of simulated topological energy Descriptors for the solid (FD, number and position of CH3-) GFA descriptive equation

Im

2-MeIm

4-MeIm

5-MeIm

2,4-MeIm

2,5-MeIm

4,5-MeIm

Experimental structures

X

*

DFT

FAU

GIS

LTA

MER

RHO

SOD

Topology Linker

Quantitative Structure Activity/Property Relationship Energy landscape of ZIFs

( )( )( )

( ),'5_*'4_*'2_*'

*

3

3

3

εεδδγγββ

α ++

+++

+=∆nbCHnbCHnbCH

FDET

Galvelis, Slater, Mellot-Draznieks et al. CrystEngComm. 2013, 15, 9603-9612. Amrouche, Creton, Siperstein and Nieto-Draghi, RSC Advances, 2012, 2, 6028.

SOD-2,4Me2Im 4-ring SOD-2,4Me2Im inter SOD-2,4Me2Im 6-ring SOD-2,4Me2Im intra

SOD-2,5Me2Im 4-ring SOD-2,5Me2Im inter SOD-2,5Me2Im intra SOD-2,5Me2Im 6-ring

Galvelis, Slater, Mellot-Draznieks et al. CrystEngComm. 2013, 15, 9603-9612.

Intra in SOD-2,4Me2Im

repulsive

An NCI analysis was performed on the seven SOD topologies with the different methyl-functionalized linkers to further understand the influence of the methyl group on the stability of this specific topology.

Intra : repulsive ie. steric clashes between substituents Inter : attractive, ie. C-H...H-C bonds between the substituents of different B(Im)4 clusters


Inter in SOD-2,4Me2Im attractive

Im-SOD

SOD-2,4Me-Im

SOD-4,5 Me-Im

C-Hmethyl...H-Im

C-Hmethyl...H-Cmethyl

- SOD 2,4-MeIm et SOD Im : fenêtre D6 plane de manière à maximiser les interactions (stabilisantes) entre substituant - SOD 4,5-MeIm : perte de la planarité : contraintes stériques entre substituants trop importante

3. Impact of the linker on the energy landscape of BIFs

-8

-6

-4

-2

0

2

4

6

8

-40 -20 0 20 40 60 80

Imidazole2Me4Me5Me24Me25Me45Me

DFT calculations

UFF

est

imat

ion

of

van

der W

aals

inte

ract

ions

DFT-D versus Forcefields?

R² = 0,9623

-40-20

020406080

-10 -5 0 5 10

RHO R² = 0,8566

-40

-20

0

20

40

60

-10 -5 0 5 10

MER

R² = 0,8973

-40

-20

0

20

40

60

-10 -5 0 5

LTA R² = 0,6808

-20

0

20

40

60

-10 -5 0 5 10

GIS R² = 0,9721

-40

-20

0

20

40

60

-10 -5 0 5

DFT

R² = 0,7397

-20

0

20

40

60

-4 -2 0 2 4 6

FAU

R² = 0,5509

-40

-20

0

20

40

-4 -2 0 2

SOD

Van de Waals contributions in ZIFs’ energy landscape:

DFT-D versus Forcefields?

SOD-2,4-MeIm SOD-Im SOD-4,5-MeIm

NCI : Non Covalent Interaction

The NCI approach: Studying weak interactions

Program NCIplot

RDG : criteria of interaction

Density : criteria of strength

Area of interactions :

Weak density and weak RGD

FAUJASITE- TYPE zeolite

Sodalite cage (β-cage)

Hexagonal prism

Supercage (α-cage)

BCT

DFT

GIS

SOD

MER

RHO

LTA

Hayashi, Coté, Furukawa, O’Keeffe, Yaghi, Nature Materials, 2007, 6, 501.


Selective adsorption @ 273K

CO2

CH4

in silico approaches in metal organic frameworks: crystal...

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