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

Abstract

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.

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

“…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.…”

Design and synthesis of coordination polymers with chelated units and their application in nanomaterials science

“…We shall notice crystal engineering of heterometallic CPs based on FeL 3 and Fe(L 0 ) 3 chelates, where L ¼ 1,3-di(4-pyridyl) propane-1,3-dionato and L 0 ¼ 1,3-di(3-pyridyl)propane-1,3dionato, which act as metalloligands in reactions with Ag salts forming CPs with [AgFeL 3 ] n and [AgFe(L 0 ) 3 ] n units (Scheme 5). 104 It is important that structure of obtained CPs depends on nature of used counter-ions. Thus, reaction between FeL 3 and AgBF 4 leads to CP, in which Ag centers link metalloligands in discrete nanotubes, while the reactions with AgPF 6 and AgSbF 6 have given CPs, in which metalloligands are bound in sheets.…”

3-(Pyridin-4-yl)acetylacetone: CdII and HgII compete for nitrogen coordination

“…1; Burrows et al, 2007;Kondracka & Englert, 2008;, 1,3-dipyridylpentane-2,4-dione [see (b) in Fig. 1; Burrows et al, 2010Burrows et al, , 2012 or 3-(pyridin-4-yl)pentane-2,4-dione, HacacPy [see (c) in Fig. 1; Chen et al, 2004;Li et al, 2011;Mackay et al, 1995;Merkens et al, 2013Merkens et al, , 2014Truong et al, 2017a,b;Vreshch et al, 2003Vreshch et al, , 2004Vreshch et al, , 2005Zhang et al, 2008], have been used successfully to assemble extended structures.…”

“…For 1,3-dipyridylpentane-2,4-dione [see (b) in Fig. 1], Burrows et al (2012) detected both tautomers in the 1 H NMR spectrum. Diffraction results show that the uncoordinated molecules HacacCN (Silvernail et al, 2001) and HacacPy (Truong et al, 2017b) adopt the enol form in the crystalline phase.…”