Topological Characterization of Coordination Networks & Metal-Organic Frameworks :

Size: px

Start display at page:

Download "Topological Characterization of Coordination Networks & Metal-Organic Frameworks :"

Ruth Terry
5 years ago
Views:

1 Madrid IUCr2011 Topological Characterization of Coordination Networks & Metal-Organic Frameworks : nets and entanglements in periodic structures L. Carlucci, G. Ciani and D. M. Proserpio DCSSI, Università degli studi di Milano- Milano - Italy V.A. Blatov Samara State University - Samara Russia and

2 Michael O Keeffe Arizona State University Tempe AZ - USA

3 Topological Characterization A. F. Wells

Three ways of drawing a feldspars the most abundant

ball and stick polyhedra net From the framework of

4 Three ways of drawing a feldspars the most abundant minerals in the earth s crust M[(Si/Al) 4 O 8 ], e.g. albite, Na(Si 3 AlO 8 ), orthoclase, K(Si 3 AlO 8 ), anorthite, Ca(Si 2 Al 2 O 8 ). ball and stick polyhedra net From the framework of alumino-silicates we get a net by removing all 2-coordinated oxygen atoms -T-O-T-

5 Enumeration of nets M. O Keeffe O (ASU) J.V. Smith (UChicago) T. Iwamoto (Tokyo) 1972 Mineralomimetic chemistry: mineralomimetic structures are represented by nets observed in minerals

6 R. Robson (Melbourne - Australia) 147 citations Scaffolding-Like Materials 953 citations Infinite Polymeric Frameworks 497 citations

7 early 90 Crystal Engineering Crystal Design Infinite Polymeric Frameworks Coordination (Polymers) Networks Organic/Inorganic Hybrid Materials Metal Organic Frameworks (MOFs) Supramolecular Architectures

8 Coordination Networks and Supramolecular networks node Ligand or H-bond or weaker interactions... Different frameworks could be obtained on changing the coordination/h-bond geometry of the nodes...

9 Metal ions: Ag, Cu, Ni, Co, Zn, Cd coordination number and geometry M M M M M Ligands donors: N, O, P, S bi/polidentate neutral/anionic Lenght rigidity/flexibility

10 Coordination Network multiply intergrown aka interpenetrated (6-fold ) underlying net: diamondoid (dia) Cu C N Kinoshita, Y., Matsubara, I., Higuchi, T. and Saito, Y. Bull. Chem. Soc. Jpn 1959, 32, 1221

11 Coordination Network with polytopic links underlying net: dia Cu C N Hoskins, B. F. and Robson, R. J. Am. Chem. Soc. 1989, 111,

12 H. Li, M Eddaoudi, M. O'Keeffe, O.M. Yaghi MOF-5 Nature 1999 MOF (Metal-Organic Framework-5) underlying net: pcu 1921 citations

13 Metal-Organic Frameworks (MOFs) 1) Cationic metal-containing clusters (secondary building units SBU) 2) Joined by organic linkers 3) Neutral frameworks 4) Robust and highly porous

14 1) Cationic metal-containing clusters (secondary building units SBU) The cluster in basic zinc acetate In the acetate each carboxylate C atom (black) is joined to a methyl group -> discrete molecule H. Koyama, Y. Saito, Bull.Chem. Soc. Japan 27, 112 (1954)

(neutral neutral framework) that is robust and highly porous.

15 In MOF-5 the basic zinc acetate clusters (SBU) are joined by ditopic linkers (terephthalate) to make an infinite crystal (neutral neutral framework) that is robust and highly porous. H. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi, Nature, 1999, 402, 276

16 net Architectural stability of MOF-5

Covalent Organic Frameworks COFs Supramolecular Architectures

17 ...end of the nineties 1998 IF 4.00 Coordination Networks Metal Organic Frameworks MOFs Covalent Organic Frameworks COFs Supramolecular Architectures Interactions Covalent, Ionic, Coordination H-bond, van der Waals CH... O, CH... π, π... π 2000 IF 4.39

18 MOF-like structures reported in the CSD (Cambridge Structural Database) Doubling time 3.6 yrs compared with 9.3 yrs for all CSD! # of structures in CSD nov

19 Reticular Chemistry Scale Chemistry O. M. Yaghi, M. O Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, J. Kim, Nature, 2003, 423, citations G. Férey, Chem. Soc. Rev. 2008, 37, citations

20 Underlying nets Standard representation: Keep only atoms with cooordination > 2 Cluster representation: Simplification of polydentate groups or SBU with centres of the same coordination N N N O N

21 simplification and rationalization... Topology is the theory of shapes which are allowed to stretch, compress, flex and bend, but without tearing or gluing 2D hexagonal honeycomb layer hcb brick wall parquet

22 SbCl 3 (p-diacetylbenzene)

23 Cationic clusters and SBUs (red) SBU = Secondary Building Unit. Blue polyhedra are Metal-O

24 Organic polytopic linkers (top) and SBUs (bottom, green)

25 Two simplest type of MOF topology MOF-5 underlying net 6-c pcu underlying net 3,4-c pto Cluster representation

26 Simplification of any periodic structure and classification of the underlying net and much more

27 dia, pcu, pto three letter symbols are RCSR symbols Reticular Chemistry Structure Resource rcsr.anu.edu.au M. O'Keeffe, M. A. Peskov, S. J. Ramsden, O. M. Yaghi Accts. Chem. Res. 2008, 41,

28 Coordination Networks & MOFs Underlying nets but which nets are more important and/or frequent and/or likely to occur?

29 Q. What are the ways of linking simple shapes (squares, tetrahedra etc.) into frameworks? A. Infinitely many Q. Of these what are the most likely targets for synthesis? A. Those with one kind of link (edge transitive) Q. How many of these? A small number: 54 edge transitive nets these are the prime targets of reticular chemistry O. Delgado-Friedrichs, M. O'Keeffe and O. M. Yaghi Acta Crystallogr. 2003, A59, 22; 2003, A59, 515; 2006, A62, 350; 2007, A63, 344

two kinds of vertex and one kind of edge equilateral triangle srs

30 5 special uninodal have regular coordination figure 15 other nets with one kind of vertex and one kind of edge 34 other nets with two kinds of vertex and one kind of edge equilateral triangle srs square nbo regular tetrahedron dia regular octahedron pcu cube bcu

31 Most frequent underlying nets CNs default nets 1 pcu 2 dia 774 MOFs 3 bcu 4 cds 5 srs 16 nbo 6620 CNs 11651

32 From Acc. Chem. Res. 2005: We feel that we discovered, rather than invented, the five regular nets. The present discovery that Nature uses these structures overwhelmingly in crystal topologies does not surprise us; rather it is the exceptions that are the occasions for thought.

33 But it s all so simple? and entanglements nets and in periodic structures Entangled: interlaced; complicated; Entanglement: intricate and confused involution interpenetration and polycatenation

34 fold dia 291 citations

1998 3021 citations Interpenetrating structures, are characterized by the presence of infinite structurally regular motifs that must

35 citations Interpenetrating structures, are characterized by the presence of infinite structurally regular motifs that must contain rings through which independent components are inextricably entangled and that can be disentangled only by breaking internal connections

36 932 citations citations 323 citations

37 interpenetration of dia nets Cuprite Cu 2 O Niggli 1922

38 Crystallographic observation: typically interpenetrated nets are generated from one independent atom What are the symmetry relations among the interpenetrated sub-nets? Can we find a systematic way to classify all the possible 3D interpenetration phenomena? YES using TOPOS.

symmetry elements Class III I (a,b,c,d) Nets related

39 Class I (a,b) Nets related only by translation Class II I I (a,b) Nets related only by non- translational symmetry elements Class III I (a,b,c,d) Nets related by translational and non-translational symmetry elements

40 Class I Nets related by translation only

41 Diamondoid-5f [Ag(1,4-butanedinitrile) 2 ](X) X= BF 4-, ClO 4-, PF 6-, AsF 6-, SbF x related by Translations Class Ia

42 Class II I Nets related only by non-translational symmetry elements

44 4 1 dia 4-fold 4 related by screw axis 4 1 Class IIb

45 Class III I (a,b,c,d) Nets related by translational AND non-translational symmetry elements

46 [ZnL 2 ](ClO 4 ) 2 (1996/2002) dia 6-fold6 related by translation AND non-translational sym. op. Class IIIa

47 Net occurrences: Leader again the default nets! dia, pcu, srs degree of interpenetration World Records fold dia CN fold dia H-bond fold srs CN

48 and now a natural question: Are these classes topologically related? i.e. can we deform one member of a class into a member of another class? For instance we know 38 examples of diamondoid coordination network that are 4-fold interpenetrated. How many are topologically distinct?

49 38 examples of dia 4-fold observed in 5 classes We get only 2 distinct topological types (work in progress)

50 Can we entangle 1D or 2D nets in a different way (topological)? Interpenetration vs. Polycatenation

52 dimensionality unchanged Inextricable Entanglement via Hopf links 1D + 1D 2D/3D 2D parallel 2D 2D inclined 3D 3D 3D increase of dimensionality Interpenetration Polycatenation

53 dimensionality unchanged: INTERPENETRATION increase of dimensionality: POLYCATENATION the whole has the SAME dimensionality of the components the whole has HIGHER dimensionality of at least one component the number of entangled components is finite (n-fold) each component is interlaced with ALL the others the number of entangled components is infinite at least one component is not interlaced with all the others the difference in not only semantic... but is topologic

TOPOS The zeolite conundrum: why there are so many hypothetical zeolites and so few are observed? N. A. Anurova, V.A. Blatov, G.D. Ilyushin, D.M. Proserpio J. Phys. Chem.

54 TOPOS The zeolite conundrum: why there are so many hypothetical zeolites and so few are observed? N. A. Anurova, V.A. Blatov, G.D. Ilyushin, D.M. Proserpio J. Phys. Chem. C, 2010, 114, Nanocluster description of intermetallics V.A. Blatov, G.D. Ilyushin, D. M. Proserpio Inorg. Chem. 2010, 49, V.A. Blatov, G.D. Ilyushin, D. M. Proserpio Inorg. Chem., 2011, 50, \libro_braga\figure\asufig.jpg

Crystal structure topology as a key for materials design: nets and entanglements in periodic structures

L. Carlucci G. Ciani Crystal structure topology as a key for materials design: nets and entanglements in periodic structures V.A. Blatov Topological Characterization A. F. Wells 1954-1979 Three ways of