We have been interested in in layered structures of dipicolinate complexes constructed by π-π...
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Transcript of We have been interested in in layered structures of dipicolinate complexes constructed by π-π...
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:
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stacking interactions
π-π stacking generally observed in bis-dipicolinates
Cation intercalation in layered anionic frameworks, Cationic ligands and assembling of complex ions
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 [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
[enH2][NiL2].3H2O
[penH2][CuL2].5H2O [bamH]2[NiL2].5H2O
[enH2][M(en)2(H2O)2].[CuL2]2.H2O [docH2][CuL2].2H2O
{[Na(H2O)2]2[CuL2].2H2O}n {[K2(H2O)7][CuL2]}n
Packing diagram of dipicolnate complexes with alkali metal ions:
{Ca(H2O)4][CuL2].2H2O}n [Mg(H2O)5][CuL2].2H2O
Inorg. Chim. Acta 363 (2010) 1479
Packing diagram showing intercalation of histidinium and ornithinium cations: (A-B-A manner)
[L-orniH2][CoL2].9H2O [L-hisH2][CuL2].5H2O
Polyhedron 30 (2011) 22
Complex Cation of Inter-layer separation (Å)
[enH2][NiL2].3H2O ethylenediamine 8.2
[pnH2][CuL2].xH2O* 1,3-propanediamine 10.4
[penH2][CuL2]. 5H2O 1,5-diaminopentane 11.2
[L-orniH2][CoL2].9H2O L-ornithine 11.5
[L-hisH2][CuL2].5H2O L-histidine 11.8
[bamH]2[CuL2].5H2O 4-amino benzyl amine 14.3
Inter-layer separation generated by amines and amino acid dications :
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][CuL2].3H2O
Adeninium ribbon in layers of complex anion
Close view of 1D zigzag adeninium ribbon with H-bond distances
Mn(II)-dipicolinate with cytosinium cations and its supramolecular architectures:
Packing diagram of [1H, 3H-cyt]2 [MnL2(H2O)].2cyt.6H2O viewed along a axis
ORTEP diagram of [1H, 3H-cyt]2
[MnL2(H2O)].2cyt.6H2O
Cryst. Growth Des. 10 (2010) 3242
Close view of tetrameric hydrogen bonded assembly of cytosine
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] 6H∙ 2O}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
(a) (b) (c)
(d)
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.
H2[NiL2].3H2OQuinoline
Solid State(HQ)2[NiL2].5H2O
(H5AQ)2[NiL2].4H2O
5-aminoquinoline
(Washed with MeOH)
Solid State
(4) (1)
(2)
We also establish the solid state cation exchange reactions shown below:
M(OAc)2 + LH2 + Cat [(CatH)(ML2)]n (nH2O)m + AcOH
When M = Mn(II) Cat = adenine m = 4 1 M = Cu(II) Cat = cytosine m = 6 2
MeOH
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Cationic sodium cluster [Na4(μ-H2O)6(H2O)10]4+
Coordination of cationic sodium cluster [Na4(μ-H2O)6(H2O)10]4+
[Mg(H2O)5] units are coordinated to dipicolnate complex
[CuL2] dianions are held I by polymeric aqua-bridged sodium cations
[Ca(H2O)4] 2+ units are bridged by the dipicolinate complex anions[CuL2] dianions are hel by polymeric
aqua-bridged potassium cations
Coordination by cationic ligands
Assembling as well as Scrambling:
Combination of copper and cobalt complex ions
Multiple cobalt containing cations and anions