UMR 7140 : Laboratoire de Tectonique Molculaire du Solide

Metallo-organic network based on [1.1.1.1]metacyclophane units : influence of the orientation and flexibility of the coordinating part on the dimensionality of the system
EHRHART Jrme, Nathalie Kyritsakas, Jean-Marc Planeix & Mir Wais Hosseini Laboratoire de Tectonique molculaire du solide, UMR 7140 4, rue Blaise Pascal 67008 Strasbourg mail : jehrhart@chimie.u-strasbg.fr

Abstrasct : The recent development of research on crystalline metal-organic frameworks (MOF) stems from the great promise brought by these materials for applications such as gas storage or catalysis. The design of these architectures based on the assembly of organic bridging molecules and metal centers still remains a challenge. One approach developed in our laboratory is based on molecular tectonics, which relies on the use of molecular building blocks with recognition sites, or tectons, which, under self assembly conditions, can organize into molecular networks to form crystalline materials which are analyzed by X-Ray diffraction. Recently, we have designed and synthesized a series of three [1.1.1.1]metacyclophanes functionalized with groups possessing nitrogen donor sites. Two of these ligands are flexible, functionalized with pyrazoles or imidazoles units, separated from the metacyclophane core by a methylene bridge, allowing the free rotation of the coordinating units. The only structural difference between them is the orientation of the nitrogen donor site. The third molecule is functionalized with a pyridine, directly bonded to the metacyclophane, offering high rigidity and pseudo-tetrahedral geometry. As a consequence of the preorganized geometry of the ligands, their self-assembly with metal salts allowed to obtain materials with different dimensionality and potential porous properties.

Design of the organic part : Functionalized [1.1.1.1]Metacyclophane.

General synthesis and properties of [1.1.1.1]-Metacyclophane. :
X X
Solvant

Mcp-Pyr : 2D Systems

CoCl2
Also formed with : CoBr2, ZnCl2, ZnBr2.

Coordination sites

CH3OCH2Cl, SnCl4
X

FUNCTIONALIZATION

Spacer

X X= H, Br, OH.

P bcn

- Rigid core, with 1,3 alternated conformation. - Ligand precursor with pseudo-tetrahedral geometry 3D preorganized core. - Spacer should be chosen: long, short, rigid, flexible easy optimisation. - Coordination site should varied.

Functionalized [1.1.1.1]- Metacyclophane :

Flexible spacer (methylene bridge)
Tetramethyl(Imidazole)
N N N N N N

a)
: Cl : Co(II) :N :C

b)

c)

Rigid spacer
Tetrapyridine
N

Fig 1. : a) view of the 2D network along y axis b) view of 3 successive layers showing the AB packing c) analogy with graphite AB layers packing.

Tetramethyl(Pyrazole)
N N

12

21
N N N N
N N

Fig 2. : a) Pore shape and dimensions b) Zoom on the pore formed between 3 successive layers.
N

Cristallisation

Cristallisation

Mcp-Pyne : 3D Systems
Cu(OAc)2
a)
:N :C
58.6 15

P-1

P-1

P -421c

X-Ray structures

b)

Mcp-Im

Mcp-Pyr

Mcp-Pyne

Interpenetration

I 41/ amd

Self-assembly with metallic salts :

-All the presented structures are obtained upon slow diffusion of the ligand in a chlorinated solvant in a solution containing the metal salt in an alcoholic solution.
:Cu(II) :O :N :C

Fig 3. : a) View along x axis of the 3D diamond type network formed b) view along x axis of the triply interdigitated packing.
a)

Mcp-Im : 0D systems

: Cl : Co(II) :N
a b b a

Channel 1 : a=a= 3 Channel 2 : b=b= 4 b)

c)

CoCl2
P21/n

:C

Bi-chelating pincer with adaptable bite angle :

102 N-Metal-N 143

Also formed with : CoBr2, Co(NO3)2, ZnCl2, ZnBr2, HgCl2, HgBr2, CuCl2, CuBr2
1. a) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; OKeeffe M.;Yaghi, O. M. Acc. Chem. Res., 2001, 34, 319. b) Kitagawa, S.; Kitaura R.; Noro, S. I.Angew. Chem. Int. Ed., 2004, 43, 2434. 2. Hosseini, M. W. Acc. Chem. Res., 2005, 38, 313. 3. a) Klein, C.; Graf, E.; Hosseini, M. W.; De Cian, A.; Kyritsakas-Gruber, N. Eur. J. Org. Chem. 2003, 395. b) Klein, C.; Graf, E.; Hosseini, M. W.; De Cian, A.; Kyritsakas-Gruber, N. Eur. J. Org. Chem. 2002, 802. c) Klein, C.; Graf, E.; Hosseini, M. W.; DeCian, A. Fischer, J. Chem.Commun. 2000, 239.

Fig 4. : a) View along z axis of the network showing two types of channel. b ) Perspective view of the channel 1. c ) Perspective view of the channel 2.

Conclusion and perspective : Synthesis of a new class of nitrogen donor

ligands of different nature and flexibility has been achieved. Association with metallic ions resulted in new crystalline materials of various dimensionalities and pore sizes and shapes. BET and ATG studies are now running to verify the reversible uptake of small molecular species and precisely determine the free space and adsorption surface.