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Intercalation and Cationic Ligands in Layered Anionic Frameworks of Dipicolinate Complexes

This study explores the structural dynamics of layered dipicolinate complexes, focusing on cation intercalation and π-π stacking interactions. We discuss various complexes, including [enH2][NiL2].3H2O and [CuL2]2.H2O, and their packing diagrams elucidate the organization of inorganic and organic layers. Also detailed are the interactions and stabilization effects of cations such as adeninium and cytosinium within these frameworks. The work aims to generalize interlayer separation, enhancing understandings of the architectural properties of these layered structures.

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Intercalation and Cationic Ligands in Layered Anionic Frameworks of Dipicolinate Complexes

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  1. Cation intercalation in layered anionic frameworks, Cationic ligands and assembling of complex ions We have been interested in in layered structures of dipicolinate complexes constructed by π-π interactions and also to generalize the interlayer separation while encapsulating organo-cations. A series of study carried out whose slides are listed below: π-π stacking generally observed in bis-dipicolinates

  2. Background: We have carried out extensive work on layered structures from anion assemblies of metal dipicolinates to encapsulate organocations [enH2][NiL2].3H2O [penH2][CuL2].5H2O [bamH]2[NiL2].5H2O [enH2][M(en)2(H2O)2].[CuL2]2.H2O [docH2][CuL2].2H2O Packing diagram of the complexes showing the [ML2]2- (ball and stick mode) as inorganic layer and amines (space filled mode) as organic layer. En = ethylenediamine, pen =1,5-pentanediamime , bam = 4-aminobenzylamine, doc = 1,8-diaminodecane Inorg. Chim. Acta 363 (2010) 1479; Inorg. Chem. Commun. 13 (2010) 350

  3. Packing diagram of dipicolnate complexes with alkali metal ions: {[K2(H2O)7][CuL2]}n {[Na(H2O)2]2[CuL2].2H2O}n {Ca(H2O)4][CuL2].2H2O}n [Mg(H2O)5][CuL2].2H2O Inorg. Chim. Acta 363 (2010) 1479

  4. Packing diagram showing intercalation of histidinium and ornithinium cations: (A-B-A manner) [L-hisH2][CuL2].5H2O [L-orniH2][CoL2].9H2O Inter-layer separation generated by amines and amino acid dications : Polyhedron 30 (2011) 22

  5. Mn(II) / Cu(II) dipicolinate with adeninium cations and their supramolecular architectures: ORTEP diagram of [1H, 9H-ade][3H,7H-ade][CuL2].3H2O Adeninium ribbon in layers of complex anion Close view of 1D zigzag adeninium ribbon with H-bond distances Cryst. Growth Des.10 (2010) 3242

  6. Mn(II)-dipicolinate with cytosinium cations and its supramolecular architectures: ORTEP diagram of [1H, 3H-cyt]2 [MnL2(H2O)].2cyt.6H2O Packing diagram of [1H, 3H-cyt]2 [MnL2(H2O)].2cyt.6H2O viewed along a axis Close view of tetrameric hydrogen bonded assembly of cytosine Cryst. Growth Des.10 (2010) 3242

  7. Stabilization of protonated adenine and cytosine cations in polymeric Mn(II) / Cu(II)-quinolinate complex and in flexible polycarboxylic systems: Cytosinium cations in layers of {[1H,3H-cyt]2[CuL2]∙6H2O}n Adeninium cations in layers of {[1H, 9H-ade]2[MnL2].4H2O}n Discrete cytosine-cytosinium assembly in layers of adipic acid Trimeric cytosine-cytosinium assembly in layers of citric acid Inorg. Chem. Commun. 13 (2010) 1244; J. Mol. Struct. 1001 (2011) 134

  8. (c) (a) (b) In the present study we have determined structures of few nickel complexes and demonstrate the stacking of (a) (HQ)2[NiL2].5H2O, (b) (H5AQ)2[NiL2].4H2O, (c) (H8HQ)2[NiL2].6H2O, (d) H2[NiL2].4H2O. ([NiL2]2- in ball and stick mode, in a-c cations are in space filled mode). Where Q = quinoline, 8HQ = 8-hydroxyquinoline, 5AQ = 5-aminoquinoline. This happens as the quinolines have greater tendency for π-stacking interactions. We also establish the solid state cation exchange reactions shown below: (d)

  9. Coordination of cationic sodium cluster [Na4(μ-H2O)6(H2O)10]4+ Cationic sodium cluster [Na4(μ-H2O)6(H2O)10]4+ Coordination by cationic ligands [Ca(H2O)4] 2+ units are bridged by the dipicolinate complex anions [CuL2] dianions are hel by polymeric aqua-bridged potassium cations [CuL2] dianions are held I by polymeric aqua-bridged sodium cations [Mg(H2O)5] units are coordinated to dipicolnate complex

  10. Assembling as well as Scrambling: Multiple cobalt containing cations and anions Combination of copper and cobalt complex ions

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