Heterobimetallic Cd(Zn)/Be coordination polymers involving pyridyl functionalized beryllium diketonates

Vreshch, Volodimir D.; Lysenko, Andrey B.; Chernega, Alexander N.; Sieler, Joachim; Domasevitch, Konstantin V.

doi:10.1016/j.poly.2005.02.023

Cited by 50 publications

(46 citation statements)

References 29 publications

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“…1, left; HacacCN; Burrows et al, 2007;Kondracka & Englert, 2008;, 1,3-di(pyridyl)acetylacetones (Burrows et al, 2010(Burrows et al, , 2012) and 3-(4-pyridyl)-2,4-pentanedione (Fig. 1, right;HacacPy;Mackay et al, 1995;Vreshch et al, 2003Vreshch et al, , 2004Vreshch et al, , 2005Chen et al, 2004;Zhang et al, 2008;Li et al, 2011; represent candidates for the engineering of extended structures. The nitrile-substituted HacacCN may essentially be regarded as an acetylacetonate; this functional group allows coordination to a broad range of di-and trivalent cations.…”

Section: Introductionmentioning

confidence: 99%

3-(4-Pyridyl)-acetylacetone – a fully featured substituted pyridine and a flexible linker for complex materials

Merkens

Truong

Englert

2014

Acta Crystallogr Sect B

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3-(4-Pyridyl)-acetylacetone (HacacPy) acts as a pyridine-type ligand towards CdX2 (X = Cl, Br, I). Chain polymers with six-coordinated metal cations are obtained from CdCl2 and with alternating five- and six-coordinated Cd centers from CdBr2. In either case, the formation of these compounds does not depend on the precise stoichiometry. In contrast, two different reaction products form with the heavier congener CdI2, namely a ligand-rich molecular complex CdI2(HacacPy)2 and a ligand-deficient one-dimensional polymer [CdI2(HacacPy)](1)(∞). Interconversion between these two iodo derivatives is possible via thermal degradation and mechanochemical synthesis. The acetylacetone moiety in HacacPy may be deprotonated and chelated to Fe(III), and the resulting complex Fe(acacPy)3 reacts analogously to a bridging polypyridine ligand towards the same Cd halides as the molecule HacacPy itself. With CdCl2 and CdBr2, isomorphous chain polymers are obtained in which the Cd cations adopt distorted octahedral coordination and one of the peripheric pyridyl groups remains uncoordinated. With CdI2, the iron complex acts as a mu3Fe(acacPy)3 bridge between tetrahedral Cd centers and gives rise to a ladder structure.

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Section: Introductionmentioning

confidence: 99%

3-(4-Pyridyl)-acetylacetone – a fully featured substituted pyridine and a flexible linker for complex materials

Merkens

Truong

Englert

2014

Acta Crystallogr Sect B

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“…3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) was prepared according to a slightly modified method by Vreshch et al [14]. Using standard Schlenk techniques, a solution of freshly distilled 4-vinylpyridine (39.0 mL, 362 mmol) in dry ethanol (2.5 mL) was added to a boiling solution of sodium (2.725 g, 118.5 mmol) and acetylacetone (73.5 mL, 712 mmol) in dry ethanol (47.5 mL) over 15 min.…”

Section: Synthesis Of 3-(2-(pyridin-4-yl)ethyl)pentane-24-dione (Hacmentioning

confidence: 99%

“…HacacPy was introduced in 1995 by Sanders and coworkers [11]. Following that report, first the groups of Domasevitch [12][13][14] and Maverick [15][16][17], later others [18], including our group [19], have used the compound in coordination chemistry. The structure of the uncoordinated ligand was established in 2017 by temperature-dependent neutron diffraction [20].…”

Section: Introductionmentioning

confidence: 99%

“…We here address the less popular ditopic acetylacetone 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen, Scheme 1). HacacPyen was synthesized by Domasevitch and coworkers [14] and used as O,O' chelating ligand for Be II ; the original authors also communicated the structure of a bimetallic chain polymer obtained by N coordination of the pyridyl rings in the Be II complex to CdCl 2 . We recently investigated the crystal structure of HacacPyen by temperature-dependent neutron diffraction and confirmed that the uncoordinated organic molecule exists as the enol tautomer [35].…”

Section: Introductionmentioning

confidence: 99%

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Argentophilic Interactions in Two AgI Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand

Terwingen

Englert

2019

Crystals

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Reactions of 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) with AgPF6 and AgBF4 afforded cationic silver complexes [Ag(HacacPyen)2]+ with essentially linear coordination of the Ag I cation by two pyridine N atoms. Rather unexpectedly, the HacacPyen ligands in the PF6- salt 1 adopt the diketo form, in contrast to the uncoordinated HacacPyen molecule, whereas the corresponding BF4- salt 2 and the majority of 3-substituted acetylacetones crystallizes as the enol tautomer. In both compounds 1 and 2, complex cations aggregate via short Ag...Ag interactions to pairs. These contacts amount to 3 . 21 Å in 1 and 3 . 26 Å or 3 . 31 Å in 2. As they are unsupported by any additional bridging ligands and correspond to the closest interionic interactions between neighbouring complex cations, they may be addressed as argentophilic interactions. The PF6- anions in 1 and the BF4- counter ions in 2 are involved in long and presumably electrostatic Ag...F contacts of ca. 2 . 9 Å. Additional coordination between Ag I and keto O atoms of symmetry-equivalent ligands occurs in 1 and leads to an extended two-periodic supramolecular structure.

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“…Use of metalloligands in the construction of metal-organic frameworks is a subject of continuing interest, [13,14] and the use of N-alkyl-functionalised diketiminate ligands in the secondary building block 4 presents a more easily accessible and more readily adaptable alternative to back-bone-functionalised acetylacetonates used for this purpose. [15][16][17][18][19][20][21] Luminescence Coordination polymer 4 is luminescent in the solid state at room temperature with an intense and broad emission band centred at 670 nm (full width at half maximum = 200 nm). The emission is short-lived and excited-state lifetimes are shorter than 30 ns (instrumental limit).…”

Section: Crystal Structuresmentioning

confidence: 99%

A Bifunctional Diketimine Ligand for Secondary Building Blocks: Formation of a 2D Copper–Zinc Coordination Polymer

et al. 2010

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Condensation of 3‐(aminomethyl)pyridine with acetylacetone in the presence of 2 equiv. of HCl affordedN,N′‐bis(3‐pyridylmethyl)‐2‐amino‐4‐imino‐pent‐2‐ene, nacnacCH2PyH, a diketimine with pendant pyridine donors.Under the same conditions, 2‐ and 4‐(aminomethyl)pyridine afforded the respective 1‐(2‐pyridyl)‐ and 1‐(4‐pyridyl)‐2,4‐dimethylpyrrol. The heteroleptic complex (nacnacCH2Py)(nacnacBn)Zn was obtained upon reaction of nacnacCH2PyH with nacnacBnZnEt. Combining 2 equiv. of this ligand with ZnEt2 afforded the homoleptic complex nacnacCH2Py2Zn. The latter forms a 2D coordination polymer upon reaction with [Cu(NCMe)4][PF6], which shows short‐lived luminescence at ambient temperature. The coordination polymer and complex (nacnacCH2Py)(nacnacBn)Zn were characterised by single‐crystal X‐ray diffraction.

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Heterobimetallic Cd(Zn)/Be coordination polymers involving pyridyl functionalized beryllium diketonates

Cited by 50 publications

References 29 publications

3-(4-Pyridyl)-acetylacetone – a fully featured substituted pyridine and a flexible linker for complex materials

3-(4-Pyridyl)-acetylacetone – a fully featured substituted pyridine and a flexible linker for complex materials

Argentophilic Interactions in Two AgI Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand

A Bifunctional Diketimine Ligand for Secondary Building Blocks: Formation of a 2D Copper–Zinc Coordination Polymer

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