Interactions between Copper(II) Complexes of Mono-, Bis-, and Tris(macrocyclic) Ligands and Inorganic or Organic Guests

Comba, Peter; Lampeka, Ya. D.; Nazarenko, Alexander Y.; Prikhod'ko, Alexander I.; Pritzkow, Hans

doi:10.1002/1099-0682(200206)2002:6<1464::aid-ejic1464>3.3.co;2-i

Cited by 5 publications

(14 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus the results obtained suggest that loss of water molecules of crystallization by the copper complex [Cu 3 L(H 2 O) 6 ](btc) 2 ·40H 2 O (I), which according to X-ray diffraction data [10] has a porous structure, is accompanied by certain changes in its crystal lattice. However, this does not lead to loss of porosity in the polycrystalline sample of this compound even after it is completely dehydrated down to [Cu 3 L](btc) 2 (III).…”

mentioning

confidence: 83%

“…It has been shown that this compound has specific sorption properties [9]. Recently we described another complex with a similar crystal structure, [Cu 3 L(H 2 O) 6 ](btc) 2 ⋅40H 2 O (I), where L is a tris(macrocyclic) ligand constructed on the basis of melamine (2,4,6-triamino-1,3,5-triazine) [10]. …”

mentioning

confidence: 99%

“…The molecular structure of this complex has been analyzed in detail in [10]; this paper is devoted to examination of its crystal lattice structure and its possible changes during dehydration/rehydration, and also a study of some adsorption properties of this compound.…”

mentioning

confidence: 99%

“…As follows from X-ray diffraction data, the copper(II) ions in complex I are found in a tetragonal bipyramidal (4N + 2O) environment formed by the nitrogen donor atoms of the macrocyclic ligand and the axial water molecules [10]. The carboxylate anions do not interact with the metal ions, but rather form hydrogen bonds with the coordinated water molecules and secondary amino groups of the macrocyclic subunits.…”

mentioning

confidence: 99%

“…Therefore it is likely that, despite the presence of 46 water molecules in the single crystal I, the analytical form of this compound after holding in air is the crystal hydrate [Cu 3 L(H 2 O) 6 ](btc) 2 ⋅9H 2 O (II) [10]. Gravimetric C D measurements showed that heating this sample at 80°C for 2 h under ordinary pressure leads to loss of 10 ± 1 water molecules, and this number does not change even when the sample is held at 100°C for 24 h. On the other hand, evacuating the sample for 1 h at 20°C leads to its complete dehydration.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Dehydration/Rehydration Processes and the Porous Structure of a Tris(Macrocyclic) Carboxylate Copper(II) Complex

et al. 2005

View full text Add to dashboard Cite

A. I. Prikhod'ko, L. V. Tsymbal, P. S. Yaremov, V. G. Il'in, and Ya. D. LampekaWe have established that the crystal hydrate of the tris(macrocyclic) complex of copper with carboxylate, with a porous structure, undergoes stepwise dehydration leading to a change in its crystal lattice structure; but even total dehydration does not lead to loss of porosity in the latter. We have studied the sorption characteristics of the dehydrated sample with respect to water, methanol, and hexane.Porous crystalline materials based on metal ions linked by organic ligands ("metal-organic frameworks," MOFs) have attracted considerable attention in recent years [1]. These materials are interesting both from the standpoint of basic research and because of their specific magnetic, optical, sorption, catalytic, and other properties [2], which makes them promising systems for practical application. Publications in recent years also suggest the possibility of using MOFs for sorption and storage of gases [3,4], including molecular hydrogen [4][5][6].A special case of MOFs is crystal hydrates constructed on the basis of azamacrocyclic complexes of copper(II) and nickel(II) and aromatic carboxylates. They form a wide range of anisotropic lattices of different dimensionalities with pores and/or channels [7]. Study of the thermal and sorption properties of such compounds has shown that many of them undergo reversible dehydration/hydration reactions with retention of the crystal lattice, and can selectively react with guest molecules. In the overwhelming majority of cases, in materials of this type the carboxylate anions act as bridging ligands linking the metal ions into one-dimensional chains or two-dimensional layers (coordination polymers). The only macrocyclic MOF with a nonpolymeric structure known today is [Ni(cl)(H 2 O) 2 ] 3 (btc) 2 ⋅24H 2 O (cl = 1,4,8,11-tetraazacyclotetradecane (cyclam); btc 3-= the anion of 1,3,5-benzenetricarboxylic acid). Interaction between the cation and the anion in the crystal lattice of this complex occurs via hydrogen bonds between water molecules coordinated to the nickel(II) ion and the ionic carboxylate [8]. It has been shown that this compound has specific sorption properties [9]. Recently we described another complex with a similar crystal structure, [Cu 3 L(H 2 O) 6 ](btc) 2 ⋅40H 2 O (I), where L is a tris(macrocyclic) ligand constructed on the basis of melamine (2,4,6-triamino-1,3,5-triazine) [10].

show abstract

mentioning

confidence: 83%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Dehydration/Rehydration Processes and the Porous Structure of a Tris(Macrocyclic) Carboxylate Copper(II) Complex

et al. 2005

View full text Add to dashboard Cite

show abstract

Bispidine Coordination Chemistry

Comba

Kerscher

Schiek

2007

Progress in Inorganic Chemistry

Self Cite

143

198

View full text Add to dashboard Cite

Encapsulation of Cyanometalates by a Tris‐macrocyclic Ligand Tricopper(II) Complex: Syntheses, Structural Variation, and Magnetic Exchange Coupling Pathways

Atanasov¹,

Comba²,

Lampeka³

et al. 2006

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The reaction of [M(CN)(6)](3-) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and [M(CN)(8)](4-/3-) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] ([Cu(3)(L)](6+)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, [Cu(3)(L)](6+) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)][M(CN)(6)](2)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated [M(CN)(6)](3-) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units. Due to the stability of the +IV oxidation state of Mo and W, only assemblies with [M(CN)(8)](4-) were obtained. The Mo(4+) and W(4+) complexes were crystallized in two different structural forms: [[Cu(3)(L)(OH(2))](2)[Mo(CN)(8)]](NO(3))(8)15 H(2)O with a structural motif that involves isolated spherical [[Cu(3)(L)(OH(2))](2)[M(CN)(8)]](8+) ions and a "string-of-pearls" type of structure [[[Cu(3)(L)](2)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O, with [M(CN)(8)](4-) ions that bridge the encapsulated octacyanometalates in a two-dimensional network. The magnetic exchange coupling between the various paramagnetic centers is characterized by temperature-dependent magnetic susceptibility and field-dependent magnetization data. Exchange between the CuCu pairs in the [Cu(3)(L)](6+) "ligand" is weakly antiferromagnetic. Ferromagnetic interactions are observed in the cyanometalate assemblies with Cr(3+), exchange coupling of Mn(3+) and Fe(3+) is very small, and the octacoordinate Mo(4+) and W(4+) systems have a closed-shell ground state.

show abstract

Interactions between Copper(II) Complexes of Mono-, Bis-, and Tris(macrocyclic) Ligands and Inorganic or Organic Guests

Cited by 5 publications

References 11 publications

Dehydration/Rehydration Processes and the Porous Structure of a Tris(Macrocyclic) Carboxylate Copper(II) Complex

Dehydration/Rehydration Processes and the Porous Structure of a Tris(Macrocyclic) Carboxylate Copper(II) Complex

Bispidine Coordination Chemistry

Encapsulation of Cyanometalates by a Tris‐macrocyclic Ligand Tricopper(II) Complex: Syntheses, Structural Variation, and Magnetic Exchange Coupling Pathways

Contact Info

Product

Resources

About