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We have been interested in in layered structures of dipicolinate complexes constructed by π-π interactions and also to generalize the interlayer separation.

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Presentation on theme: "We have been interested in in layered structures of dipicolinate complexes constructed by π-π interactions and also to generalize the interlayer separation."— Presentation transcript:

1 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 Cation intercalation in layered anionic frameworks, Cationic ligands and assembling of complex ions

2 Background: We have carried out extensive work on layered structures from anion assemblies of metal dipicolinates to encapsulate organocations 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 [enH 2 ][NiL 2 ].3H 2 O [penH 2 ][CuL 2 ].5H 2 O[bamH] 2 [NiL 2 ].5H 2 O [enH 2 ][M(en) 2 (H 2 O) 2 ].[CuL 2 ] 2.H 2 O [docH 2 ][CuL 2 ].2H 2 O

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

4 Packing diagram showing intercalation of histidinium and ornithinium cations: (A-B-A manner) [L-orniH 2 ][CoL 2 ].9H 2 O [L-hisH 2 ][CuL 2 ].5H 2 O Polyhedron 30 (2011) 22 ComplexCation ofInter-layer separation (Å) [enH 2 ][NiL 2 ].3H 2 Oethylenediamine8.2 [pnH 2 ][CuL 2 ].xH 2 O*1,3-propanediamine10.4 [penH 2 ][CuL 2 ]. 5H 2 O1,5-diaminopentane11.2 [L-orniH 2 ][CoL 2 ].9H 2 OL-ornithine11.5 [L-hisH 2 ][CuL 2 ].5H 2 OL-histidine11.8 [bamH] 2 [CuL 2 ].5H 2 O4-amino benzyl amine14.3 Inter-layer separation generated by amines and amino acid dications :

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

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

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 [CuL 2 ]∙6H 2 O} n Adeninium cations in layers of {[1H, 9H-ade] 2 [MnL 2 ].4H 2 O}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 (2011) 134

8 (a) (b) (c) (d) In the present study we have determined structures of few nickel complexes and demonstrate the stacking of (a) (HQ) 2 [NiL 2 ].5H 2 O, (b) (H5AQ) 2 [NiL 2 ].4H 2 O, (c) (H8HQ) 2 [NiL 2 ].6H 2 O, (d) H 2 [NiL 2 ].4H 2 O. ([NiL 2 ] 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:

9

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

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


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