Synthesis and structure of [18-MCCuII(N)pko-6]6+: A new member of anion encapsulating metallamacrocyles

doi:10.1016/j.inoche.2005.09.024

Inorganic Chemistry Communications

Volume 8, Issue 12, December 2005, Pages 1173-1176

https://doi.org/10.1016/j.inoche.2005.09.024 Get rights and content

Abstract

The reaction of copper(II) perchlorate with di-2-pyridyl ketone oxime yields the first 18-MC-6 complex with M–N–O connectivity, [Cu₆(pko)₆ClO₄(CH₃CN)₆] [Cu₆(pko)₆(ClO₄)₃(CH₃CN)₄] · 8ClO₄ · 14CH₃CN · H₂O 1. In the solid state the cationic complex encapsulates a perchlorate anion within the central cavity. Magnetic susceptibility measurements reveal that the complex is diamagnetic. EPR measurements indicate that the complex dissociates in DMF.

Graphical abstract

The 18-metallacrown-6 complex with a repeat unit of –[Cu–N–O]₆– encapsulates a perchlorate anion in the solid state. Pyridyl rings from the ligand form a cavity above (dark color) and below (light color) the metallacrown ring and help to encapsulate the perchlorate anion.

Section snippets

Acknowledgments

This work was supported by NSF CHE-0111428 to V.L.P. and PYTHAGORAS II to D.P.K.

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A 2-D metal-organic framework of the iron-based 18-metallacrown-6 with N-(methyl-maleamic ester) terminal ligand
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Citation Excerpt :
While based on dihydrazide derivatives, the other type of MCs with [M–N–N] repeat units (azametallacrown, azaMC) was synthesized. The rings of azaMCs have been expanded to 18-MC-6 [4–6,7b], 24-MC-8 [7], 30-MC-10 [7b,8], 36-MC-12 [9], 45-MC-15 [10], 48-MC-16 [11], even to 60-MC-20 [12]. Also, the ligands, such as salicylaldehyde-2-pydinecarboxylhydrazone, 3, 5-diphenylpyrazolate or derivatives of 1, 2, 4-triazoe, have been used for the preparation of azaMCs [13].
An 18-membered complex, [Fe(MMSHZ)(DMF)]6 (1) [MMSHZ = N-(methyl-maleamic ester)acylsalicylhydrazine] was synthesized and structurally characterized. There are not only particular geometry configurations of N-terminal groups which result in the unique shape of the centric cavity, but also inter- and intra-molecular interactions assembling adjacent molecules into 2-D framework in complex 1. Temperature-dependent magnetic susceptibility measurements indicate that this complex exhibits significantly antiferromagnetic coupling among the metal centers.
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The use of di-2-pyridyl ketone oxime, (py)pkoH, and phenyl 2-pyridyl ketone oxime, ppkoH, in copper(II) hexafluoroacetylacetonate chemistry is reported. The reaction of CuCl₂·2H₂O with one and two equivalents of ppkoH and Na(hfac), respectively, in CH₂Cl₂ affords the dinuclear complex [Cu₂(hfac)₂(ppko)₂] (1) in excellent yield. The replacement of ppkoH by (py)pkoH gives the isostructural compound [Cu₂(hfac)₂{(py)pko}₂] (2) in good yield. The Cu^II atoms in both 1 and 2 are doubly bridged by the oximate groups of two η¹:η¹:η¹:μ₂ ppko⁻ and (py)pko⁻ ligands, respectively. The bridging Cu–(R–NO)–Cu′ units are not planar, with the torsion angles being 23.2° (1) and 20.3° (2). A bidentate chelating hfac⁻ ligand completes five-coordination at each square pyramidal metal ion. The hfac⁻-free reaction system CuCl₂·2H₂O/(py)pkoH/NEt₃ (1:2:1) gives instead the mononuclear complex [CuCl{(py)pko}{(py)pkoH}] (3) in very good yield. The Cu^II atom is coordinated by two N,N′-bidentate (py)pko⁻/(py)pkoH chelates and a monodentate chloride anion resulting in a distorted square pyramidal geometry around the metal center. Variable-temperature, solid-state dc magnetic studies were carried out on the representative dinuclear complex 1 in the 2.0–300 K range. The data indicate a very strong antiferromagnetic exchange interaction and a resulting S = 0 ground state, which is well isolated from the S = 1 excited state. The J value of −720 cm⁻¹ was derived from the fitting of the experimental data using the Hamiltonian H = −J(S₁ · S₂).
A mixed-type of azametallacrown containing [Mn<inf>6</inf>(pnhz)<inf>6</inf>(DMF)<inf>4</inf>(H<inf>2</inf>O)<inf>2</inf>] and [Mn<inf>6</inf>(pnhz)<inf>6</inf>(DMF)<inf>2</inf>(H<inf>2</inf>O)<inf>4</inf>] constructed by a flexible pentadentate ligand
2010, Inorganic Chemistry Communications
A mixed-type of azametallacrown based on a flexible pentadentate N-propionyl ligand was reported, which exhibits not only the completely different arrangement of the metal centers but also diversely geometric configurations of the N-terminal ligands, and this complex can further assemble into a novel 3-D supramolecular structure using two different aza18-MC-6 as secondary building units (SBUs) via the intermolecular C–H⋯π, π–π and C–H⋯O interactions. Temperature-dependent magnetic susceptibility measurements of the title complex indicate that the complex presents significantly antiferromagnetic coupling among metal centers.

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Synthesis and structure of [18-MCCuII(N)pko-6]6+: A new member of anion encapsulating metallamacrocyles

Abstract

Graphical abstract

Section snippets

Acknowledgments

J. Am. Chem. Soc.

Proc. Nat. Acad. Sci.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Inorg. Chem.

Inorg. Chem.

J. Am. Chem. Soc.

Coordin. Chem. Rev.

Supramol. Chem.

Inorg. Chem.

Angew. Chem., Int. Ed. Engl.

Inorg. Chem.

Synthesis and structure of $[18 - {MC}_{{Cu}^{II} (N) pko} - 6]^{6 +}$ : A new member of anion encapsulating metallamacrocyles