Dipyridyl β-diketonate complexes: versatile polydentate metalloligands for metal–organic frameworks and hydrogen-bonded networks

Burrows, Andrew D.; Frost, Christopher G.; Mahon, Mary F.; Raithby, Paul R.; Renouf, Catherine L.; Richardson, Christopher; Stevenson, Anna J.

doi:10.1039/c0cc00646g

Cited by 52 publications

(33 citation statements)

References 30 publications

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“…This was confirmed in reports about the coordination chemistry of the mono-pyridyl ligands a [10][11][12][13][14] and b, 15 and of the di-pyridyl derivative c. 16, 17 3-Ĳ4-Pyridyl)acetylacetone (Scheme 1, a) has also been employed in halogen-and hydrogen-bonded extended structures. In addition, the pyridine derivatives in Scheme 1 (ligands a-c) behave as good N nucleophiles to metal cations.…”

Section: Introductionsupporting

confidence: 57%

Crosslinking of the Pd(acacCN)₂ building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Guo

Merkens

et al. 2015

CrystEngComm

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After deprotonation, the acetylacetonate moiety of the ditopic ligand 3-cyanoacetylacetone (HacacCN) acts as a chelating ligand towards PdĲII). The resulting square-planar complex PdĲacacCN) 2 represents a suitable building unit for extended structures via coordination of AgĲI) cations to the peripheral nitrile groups. These target compounds have been structurally characterized: with silver salts of the anions BF 4 − , ClO 4 − , PF 6 − and CF 3 SO 3 − , chain polymers with an alternating sequence of PdĲII) and AgĲI) are obtained. Solvent molecules and counter anions fill voids close to the silver cations; more weakly coordinating anions are engaged in longer, the triflate anion in a shorter interaction to AgĲI). In contrast to powder samples, larger crystals of these one-dimensional polymers are rather stable with respect to desolvation. Two isomorphous 1D structures undergo a fully reversible k 2 phase transition which can be monitored by single crystal diffraction. The phase transition temperature depends on the nature of the counter anion and may therefore be tuned as a function of chemical composition. The formation of chain polymers by linking PdĲacacCN) 2 building blocks with AgĲI) salts of BF 4 − , ClO 4 − , PF 6 − and CF 3 SO 3 − follows chemical intuition whereas its reaction with silver nitrate leads to an unexpected and close-packed 3D structure in which layers of composition AgĲNO 3 ) are connected by PdĲacacCN) 2 linkers. CrystEngComm This journal is ; Tel: +1 612 8021080† Electronic supplementary information (ESI) available: Crystallographic information in CIF format, displacement ellipsoid plots for 1-7, powder patterns for 2, 3, 5 and 7, intensity ratio IĲ f/t) for 2 and 3 over larger temperature ranges, intensity of single reflections in 2, 3 and 4, 19 F NMR result of 4 and sequence of slides visualizing the phase transition in 2.

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Section: Introductionsupporting

confidence: 57%

Crosslinking of the Pd(acacCN)₂ building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Guo

Merkens

et al. 2015

CrystEngComm

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“…Eu(Hdppd)3 (H 2 dppd)]Cl 4 ·EtOH reported earlier,16 reveal it is possible to coordinate between two and four dppd or dmppd ligands to a metal centre, depending on the size and coordination preference of the metal centre, though the reaction conditions also have a significant effect on the product isolated from the reaction. Although, at first sight, the ligands might appear to be relatively rigid, there is considerable flexibility in theirconformations, evidenced largely by the wide range of fold angles observed as a consequence of bending about the ligand O!!…”

mentioning

confidence: 82%

“…14,15 We recently communicated the use of the 1,3-di(4-pyridyl)propane-1,3-dionato ligand (dppd) to prepare the octahedral complexes [Al(dppd) 3 ] 3 and [Ga(dppd) 3 ]. 16 These compounds are metalloligands containing six exotopic pyridyl groups, so have the potential to act as octahedral nodes. We demonstrated that reaction of these complexes with silver(I) nitrate gave [Ag 3 M(dppd) 3 ](NO 3 ) 3 !xDMSO (M = Al, Ga), in which the silver centres bridge between metalloligands leading to interpenetrated cubic networks.…”

Section: Introductionmentioning

confidence: 99%

Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks

et al. 2012

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The iron(III) and aluminium(III) complexes of 1,3-di(4-pyridyl)propane-1,3-dionato (dppd) and 1,3-di(3-pyridyl)propane-1,3-dionato (dmppd), [Fe(dppd)(3)] 1, [Fe(dmppd)(3)] 2, [Al(dppd)(3)] 3 and [Al(dmppd)(3)] 4 have been prepared. These complexes adopt molecular structures in which the metal centres contain distorted octahedral geometries. In contrast, the copper(II) and zinc(II) complexes [Cu(dppd)(2)] 5 and [Zn(dmppd)(2)] 6 both form polymeric structures in which coordination of the pyridyl groups into the axial positions of neighbouring metal centres links discrete square-planar complexes into two-dimensional networks. The europium complex [Eu(dmppd)(2)(H(2)O)(4)]Cl·2EtOH·0.5H(2)O 7 forms a structure containing discrete cations that are linked into sheets through hydrogen bonds, whereas the lanthanum complex [La(dmppd)(3)(H(2)O)]·2H(2)O 8 adopts a one-dimensional network structure, connected into sheets by hydrogen bonds. The iron complexes 1 and 2 act as metalloligands in reactions with silver(I) salts, with the nature of the product depending on the counter-ions present. Thus, the reaction between 1 and AgBF(4) gave [AgFe(dppd)(3)]BF(4)·DMSO 9, in which the silver centres link the metalloligands into discrete nanotubes, whereas reactions with AgPF(6) and AgSbF(6) gave [AgFe(dppd)(3)]PF(6)·3.28DMSO 10 and [AgFe(dppd)(3)]SbF(6)·1.25DMSO 11, in which the metalloligands are linked into sheets. In all three cases, only four of the six pyridyl groups present on the metalloligands are coordinated. The reaction between 2 and AgNO(3) gave [Ag(2)Fe(dmppd)(3)(ONO(2))]NO(3)·MeCN·CH(2)Cl(2)12. Compound 12 adopts a layer structure in which all pyridyl groups are coordinated to silver centres and, in addition, a nitrate ion bridges between two silver centres. A similar structure is adopted by [Ag(2)Fe(dmppd)(3)(O(2)CCF(3))]CF(3)CO(2)·2MeCN·0.25CH(2)Cl(2)13, with a bridging trifluoroacetate ion playing the same role as the nitrate ion in 12.

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“…Geometric considerations apart, their inequivalent donor sites may favor the coordination of different metal centers: acetylacetone derivatives with N donor substituents combine coordination sites of different Pearson hardness (Pearson, 1997): 3-cyano-2,4-pentanedione ( Fig. 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.…”

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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Dipyridyl β-diketonate complexes: versatile polydentate metalloligands for metal–organic frameworks and hydrogen-bonded networks

Cited by 52 publications

References 30 publications

Crosslinking of the Pd(acacCN)₂ building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Crosslinking of the Pd(acacCN)₂ building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks

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

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Dipyridyl β-diketonate complexes: versatile polydentate metalloligands for metal–organic frameworks and hydrogen-bonded networks

Cited by 52 publications

References 30 publications

Crosslinking of the Pd(acacCN)2 building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Crosslinking of the Pd(acacCN)2 building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks

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

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Crosslinking of the Pd(acacCN)₂ building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network

Crosslinking of the Pd(acacCN)₂ building unit with Ag(i) salts: dynamic 1D polymers and an extended 3D network