Cation intercalation in layered anionic frameworks Cationic ligands

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

Background: We have carried out extensive work on layered structures from anion assemblies of metal dipicolinates to encapsulate organocations [en. H 2][Ni. L 2]. 3 H 2 O [pen. H 2][Cu. L 2]. 5 H 2 O [en. H 2][M(en)2(H 2 O)2]. [Cu. L 2]2. H 2 O [bam. H]2[Ni. L 2]. 5 H 2 O [doc. H 2][Cu. L 2]. 2 H 2 O Packing diagram of the complexes showing the [ML 2]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

Packing diagram of dipicolnate complexes with alkali metal ions: {[Na(H 2 O)2]2[Cu. L 2]. 2 H 2 O}n {[K 2(H 2 O)7][Cu. L 2]}n {Ca(H 2 O)4][Cu. L 2]. 2 H 2 O}n [Mg(H 2 O)5][Cu. L 2]. 2 H 2 O Inorg. Chim. Acta 363 (2010) 1479

Packing diagram showing intercalation of histidinium and ornithinium cations: (A-B-A manner) [L-his. H 2][Cu. L 2]. 5 H 2 O [L-orni. H 2][Co. L 2]. 9 H 2 O Inter-layer separation generated by amines and amino acid dications : Complex Cation of Inter-layer separation (Å) [en. H 2][Ni. L 2]. 3 H 2 O ethylenediamine 8. 2 [pn. H 2][Cu. L 2]. x. H 2 O* 1, 3 -propanediamine 10. 4 [pen. H 2][Cu. L 2]. 5 H 2 O 1, 5 -diaminopentane 11. 2 [L-orni. H 2][Co. L 2]. 9 H 2 O L-ornithine 11. 5 [L-his. H 2][Cu. L 2]. 5 H 2 O L-histidine 11. 8 [bam. H]2[Cu. L 2]. 5 H 2 O 4 -amino benzyl amine 14. 3 Polyhedron 30 (2011) 22

Mn(II) / Cu(II) dipicolinate with adeninium cations and their supramolecular architectures: ORTEP diagram of [1 H, 9 H-ade][3 H, 7 Hade][Cu. L 2]. 3 H 2 O Adeninium ribbon in layers of complex anion Close view of 1 D zigzag adeninium ribbon with H-bond distances Cryst. Growth Des. 10 (2010) 3242

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

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

(a) (b) (c) In the present study we have determined structures of few nickel complexes and demonstrate the stacking of (a) (HQ)2[Ni. L 2]. 5 H 2 O, (b) (H 5 AQ)2[Ni. L 2]. 4 H 2 O, (c) 2(H 8 HQ)2[Ni. L 2]. 6 H 2 O, (d) H 2[Ni. L 2]. 4 H 2 O. ([Ni. L 2] in ball and stick mode, in a-c cations are in space filled mode). Where Q = quinoline, 8 HQ = 8 -hydroxyquinoline, 5 AQ = 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)

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

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