Interaction of an extended series of N-substituted di(2-picolyl)amine derivatives with copper(II). Synthetic, structural, magnetic and solution studies

Antonioli, Bianca; Büchner, B.; Clegg, Jack K.; Gloe, Kerstin; Gloe, Karsten; Götzke, Linda; Heine, A.; Jäger, Anne; Jolliffe, Katrina A.; Kataeva, О. N.; Kataev, V.; Klingeler, R.; Krause, Tilo; Lindoy, Leonard F.; Popa, A.; Seichter, Wilhelm; Wenzel, Marco

doi:10.1039/b901832h

Cited by 47 publications

(28 citation statements)

References 65 publications

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“…Although the overall situation is far from straightforward, extractant lipophilicity along with strength of metal binding are two factors known to have a major influence on the efficiency of metal ion extraction in two phase systems of the present type. [1,6,7] As an aside, it is noted that the composition of the extracted Ag I complexes employing L 1 -L 3 determined by separate (single metal) silver ion extraction experiments was in each case 1 : 1, demonstrating that significant differences exist between the solution and solid state behaviour of these systems.…”

Section: Fig 2 Ortepmentioning

confidence: 99%

Selective Solvent Extraction of Silver(I) by Tris-Pyridyl Tripodal Ligands and X-Ray Structure of a Silver(I) Coordination Polymer Incorporating One Such Ligand

et al. 2015

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Two tripodal ligands, each derived from 1,1,1-tris(hydroxymethyl)ethane and terminated respectively by 4-pyridyl (L 1 ) and 2-pyridyl groups (L 2 ), have been synthesised. Competitive seven-metal extraction studies (H 2 O/CHCl 3 ) incorporating equal concentrations of cobalt(II), nickel(II), copper(II), zinc(II), silver(I), cadmium(II), and lead(II) in the aqueous phase and L 1 or L 2 in the organic phase showed selective extraction of silver(I) in each case. A parallel solvent extraction experiment involving a related tripodal tris-pyridyl ligand (L 3 ) based on a 1,3,5-substituted aryl ring scaffold and incorporating thioether sulfurs in each tripod arm also showed extraction selectivity for silver(I); extraction efficiencies towards this metal ion fall in the order L 3 . L 1 . L 2 . Physical data are in accord with L 1 forming a capsule-like complex of type [Ag 3 L 1 2 ] 3þ in which silver ions link pairs of pyridyl groups from different ligands. In contrast, L 2 yields a complex of type [Ag 2 L 2 (NO) 3 ] n whose X-ray structure showed it to be a two-dimensional coordination polymer in which the three pyridyl donors of each L 2 coordinate to three silver(I) centres, two of which are crystallographically distinct, with the centres also bonded to bidentate and/or bridging bidentate nitrato groups.

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Section: Fig 2 Ortepmentioning

confidence: 99%

Selective Solvent Extraction of Silver(I) by Tris-Pyridyl Tripodal Ligands and X-Ray Structure of a Silver(I) Coordination Polymer Incorporating One Such Ligand

et al. 2015

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“…A careful examination of the reported copper (II) complexes involving double µ-dichlorido bridges and a distorted octahedral coordination geometry, reveals that they all display discrete dinuclear structures and asymmetrical bridges characterized by two different Cu-Cl distances [28][29][30][31][32][33][34][35]. The shortest distance corresponds to a normal Cu-Cl bond length and does not show any significant variation from complex to complex (2.218-2.278 Å); while the longest one shows a large deviation (2.698-3.112 Å).…”

Section: -Zmentioning

confidence: 99%

Polypyridyl-based Cu(II) coordination polymers: Synthesis, structural and magnetic characterizations

et al. 2015

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International audienceNew Cu(II) coordination polymeric neutral chains of formula [Cu 2 (1,4-tpbd)Cl 2 L 2)] (1,4-tpbd = N,N,N'N'-tetrakis(2-pyridylmethyl)benzene-1,4-diamine, L = 1,1,3,3-tetracyano-2-ethoxypropenide (tcnoet)-(1) or 1,1,3,3-tetracyano-2-propoxypropenide (tcnopr)-(2)) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction and magnetic measurements. The crystal structure determinations of 1 and 2 reveal in both cases a one-dimensional structure in which the 1,4-tpbd acts as a bis-chelating ligand and the two chloride anions as asymmetrical bridging ligands. The Cu···Cu distances through the bis-chelating 1,4-tpbd ligand (8.194(1) and 8.245(3) Å for 1 and 2 respectively) are in the range of the corresponding distances observed for parent complexes involving similar bridges; and as expected, the Cu···Cu distances through the asymmetrical ( 2-Cl) 2 bridges are significantly shorter (4.021(2) and 4.125(2) Å for 1 and 2, respectively). For both compounds, magnetic measurements exhibit a maximum in the  m vs. T plot (at 50 K for 1, and at 48 K for 2), characteristic of antiferromagnetic exchange interactions occurring mainly through the tbpd organic ligand that can be very well reproduced with a S = ½ dimer model with g = 2.114, J =-41.2 cm-1 for 1 and g = 2.105 and J =-39.3 cm-1 for 2.

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“…The structure of 2 is seen in Figure 7. The Hg II in 2 might be described as 5-coordinate if one included the very long Hg-N(2) bond of 2.788(3) Å to the central sp 3 hybridized N of the adpa ligand, which is much longer than the more normal Hg-N(1) [11,37], but all other evidence, including a large number of solid state structures of Cu II complexes of sensors similar to adpa, such as hcdpa (Fig. 1) [38] suggests that Cu II has a very strong ability to form π complexes.…”

Section: Structure Of [Hg(adpa)i 2 ] (2)mentioning

confidence: 99%

Effects of anion coordination on the fluorescence of a photo-induced electron transfer (PET) sensor complexed with metal ions

et al. 2017

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Whether π contacts between the fluorophore of the photoinduced electron transfer (PET) sensor adpa ((N-(9-anthracenylmethyl)-N-(2-pyridinylmethyl)-2-pyridinemethanamine) and complexed metal ions or coordinated halide ions control the fluorescence intensity of adpa is further investigated via fluorescence, absorbance and density functional theory (DFT) studies. Three metal-adpa complexes were studied and the crystal structures of [Cd(adpa)I 2 ] (1), [Hg(adpa)I 2 ] (2), [Zn(adpa)Cl 2 ](H 2 O) 2 (3) and [Cd(adpa)S 2 O 3 ] 2 (4) are reported. Unlike Cl-, Br-, SCNand S 2 O 3 2-, which cause an increase in fluorescence intensity upon binding to Cd II (adpa) due to the disruption of metal-fluorophore π contacts, coordination of Ito the Cd II (adpa) complex strongly decreases fluorescence intensity. The same trend was found with the addition of Ito the Hg II (adpa) and Zn II (adpa) complexes. However, the causes of fluorescence quenching associated with three metal complexes are not necessarily the same. The structure of 3 shows that the anthracenyl fluorophore does not form a π contact with the Zn, relating to the strong CHEF (chelation enhanced fluorescence) effect Zn II shows with adpa. The absorbance study suggests that the fluorescence quenching of the Zn II (adpa) complex with Iaddition is due to collisional quenching. Fluorescence quenching in the Hg(adpa)I 2 complex is attributed to the long Hg-N bond of 2.788 Å to the central N donor of the adpa in 2, which causes quenching by a PET effect from the weakly coordinated N donor. The quenching mechanism associated with the Cd II (adpa)I 2 complex seems to be more subtle. Structure 1 shows the nearest Cd•••C distance to the anthracenyl fluorophore of adpa of 3.554 Å, where such long distances are usually associated with increases in fluorescence intensity, rather than quenching. Density functional theory (DFT) studies showed that there is structural change in the excited state of the Cd II (adpa)I 2 complex, which triggers a reordering of frontier molecular orbitals. This leads to the involvement of charge transfer from the fluorophore to the iodine in the S 1  S 0 transition, which is forbidden.

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Interaction of an extended series of N-substituted di(2-picolyl)amine derivatives with copper(II). Synthetic, structural, magnetic and solution studies

Cited by 47 publications

References 65 publications

Selective Solvent Extraction of Silver(I) by Tris-Pyridyl Tripodal Ligands and X-Ray Structure of a Silver(I) Coordination Polymer Incorporating One Such Ligand

Selective Solvent Extraction of Silver(I) by Tris-Pyridyl Tripodal Ligands and X-Ray Structure of a Silver(I) Coordination Polymer Incorporating One Such Ligand

Polypyridyl-based Cu(II) coordination polymers: Synthesis, structural and magnetic characterizations

Effects of anion coordination on the fluorescence of a photo-induced electron transfer (PET) sensor complexed with metal ions

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