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interpenetration, polycatenation, polythreading, polyknotting and more . . . in coordination network chemistry

interpenetration, polycatenation, polythreading, polyknotting and more . . . in coordination network chemistry. Università di Milano Dipartimento di Chimica Strutturale e Stereochimica Inorganica. Lucia Carlucci Gianfranco Ciani Davide M. Proserpio. 1998 Batten and Robson

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interpenetration, polycatenation, polythreading, polyknotting and more . . . in coordination network chemistry

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  1. interpenetration, polycatenation, polythreading, polyknotting and more . . .in coordination network chemistry

  2. Università di Milano Dipartimento di Chimica Strutturale e Stereochimica Inorganica Lucia Carlucci Gianfranco Ciani Davide M. Proserpio

  3. 1998 Batten and Robson 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” 1D 2D parallel2D inclined 3D

  4. Geometrical requirement for Inextricable Entanglement “Topological” Entanglement “Euclidean” Entanglement

  5. Polythreading “Euclidean” Entanglement [Ag2(bix)3](NO3)2Robson group, 1997 H2(p-COO)TPP[Ca2(H2O)8]Suslick group, 2002

  6. increase of dimensionality dimensionality unchanged Interpenetration Polycatenation Inextricable Entanglement via Hopf links 1D + 1D  2D/3D 2D parallel  2D2D inclined  3D 3D  3D “Topological” Entanglement

  7. N of entangled motifs is finite (n-fold) N of entangled motifs is infinite Each motif is interlaced with ALL the others Each motif is NEVER interlaced with all the others Interpenetration Polycatenation infinite periodic SAME dimensionality of the components BIGGER dimensionality than components components 2D or 3D nets components 0D, 1D or 2D

  8. Interpenetration

  9. [Cd2(bpethy)3](NO3)42D // 2D 2D-3f Interpenetration 63

  10. Polycatenation [Zn2(bpethy)3](NO3)2 infinite n of 1D ladders  3D blue ladders never interlaced(same for red)

  11. Doc = ‘degree of catenation’ Polycatenation Doc = ( 2 / 2 ) 2 motifs

  12. 3D infinite n of 1D ladders 2D [Cu2(MeCN)2L3](PF6)2 Schröder group, 1997 [Cd(L)1.5](NO3)2 Fujita group, 1995 Doc = (4/4) 2 motifs Doc = 4 1 motif

  13. ‘inclined’ interlocking mode [Cu2(pyz)3](SiF6)Zaworotko group, 1994 [Ag2(H2L)3 (cucurbituril)3](NO3)8 K. Kim group, 1997 Doc = (1/1) Doc = (2/2)

  14. [Ni6(bpe)10(H2O)16](SO4)6.nH2O 44

  15. 20%voids [Ni6(bpe)10(H2O)16](SO4)6.nH2O 3 motifs: Doc = ( 2 / 4 / 4 )

  16. ‘parallel’ interlocking mode [Cu(bpethe)1.5(PPh3)](PF6)S.W. Keller group, 2001 Index of separation: Is = 1 1 motif Doc = 2

  17. “Topological” Entanglement “Euclidean” Entanglement Interpenetration Polycatenation Polyknotting(self-penetrating networks) Polythreading

  18. …2D or 3D Entanglement via Borromean links?….

  19. … Borromean layers? 2D // 2D  2D (63) [Cu2(tmeda)2{Au(CN)2}3](ClO4)D.B. Leznoff et al., IC 2001 [{Ni(cyclam)}3(TCPEB)]2M. P. Suh et al., IC 2003 [K(K.2.2.2)]I(1,8-diiodoperfluorooctane)1.5I...I- P. Metrangolo et al., CG&D 2003

  20. 3-Borromean layers 2D // 2D 2D

  21. 2D // 2D  2D NOT interpenetrated nor catenated Doc = 0 Is = 1 Borromean Entanglements

  22. … n-Borromean networks? [Ag2(H2L)3](NO3)2M.L. Tong et al., Angew 1999 [Ag2L3(OH)](ClO4)S. Muthu et al., Dalton 2002

  23. … Borromean layers... 2D // 2D ... (63) undulated layer

  24. n-Borromean 3D network 2D // 2D 3D Doc = 0 Is = 1 n-Borromean 1D chain...

  25. Entanglements in n-Borromean chains : the Brunnian property

  26. Coordination polymers Supramolecular networks Metal-organic frameworks Borromean entanglements Polycatenation Interpenetration “Topological” “Euclidean” Polyknotting Polythreading A new complexity of the solid state

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