P1254325868vSaDA

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interpenetration, polycatenation,
polythreading, polyknotting and more . . .in
coordination network chemistry
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Università di Milano Dipartimento di Chimica
Strutturale e Stereochimica Inorganica
Lucia Carlucci Gianfranco Ciani Davide M.
Proserpio
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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
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Geometrical requirement for Inextricable
Entanglement
Euclidean Entanglement
Topological Entanglement
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Polythreading
Euclidean Entanglement
Ag2(bix)3(NO3)2 Robson group, 1997
H2(p-COO)TPPCa2(H2O)8Suslick group, 2002
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Inextricable Entanglement via Hopf links
1D 1D ? 2D/3D 2D parallel ? 2D 2D inclined ?
3D 3D ? 3D
Topological Entanglement
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Interpenetration
Polycatenation
infinite periodic
BIGGER dimensionality than components
SAME dimensionality of the components
components 2D or 3D nets
components 0D, 1D or 2D
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Interpenetration
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Interpenetration
Cd2(bpethy)3(NO3)4 2D // 2D ? 2D-3f
63

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Polycatenation
Zn2(bpethy)3(NO3)2
infinite n of 1D ladders ? 3D
blue ladders never interlaced (same for red)
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Doc degree of catenation
Polycatenation
Doc ( 2 / 2 )
2 motifs
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infinite n of 1D ladders
3D
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
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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)
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Ni6(bpe)10(H2O)16(SO4)6.nH2O
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Ni6(bpe)10(H2O)16(SO4)6.nH2O
3 motifs Doc ( 2 / 4 / 4 )
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parallel interlocking mode
Cu(bpethe)1.5(PPh3)(PF6) S.W. Keller group,
2001
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Topological Entanglement
Euclidean Entanglement
Interpenetration
Polycatenation
Polyknotting(self-penetrating networks)
Polythreading
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2D or 3D Entanglement via Borromean links?.
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Borromean layers?
2D // 2D ? 2D
(63)
Cu2(tmeda)2Au(CN)23(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., CGD 2003
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3-Borromean layers
2D // 2D ? 2D
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2D // 2D ? 2D NOT interpenetrated nor catenated
Doc 0 Is 1
Borromean Entanglements
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n-Borromean networks?
Ag2(H2L)3(NO3)2 M.L. Tong et al., Angew 1999
Ag2L3(OH)(ClO4)S. Muthu et al., Dalton 2002
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(63) undulated layer
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n-Borromean 1D chain...
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Entanglements in n-Borromean chains the
Brunnian property
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Coordination polymers Supramolecular
networks Metal-organic frameworks
Borromean entanglements
Polycatenation
Interpenetration
Topological
Euclidean
Polythreading
Polyknotting
A new complexity of the solid state