Unusual trinuclear complex of copper(II) containing a 4′-(3-methyl-2-thienyl)-4,2′:6′,4″-terpyridine ligand. Structural, spectroscopic, electrochemical and magnetic properties

Toledo, Dominique; Ahumada, Guillermo; Manzur, Carolina; Roisnel, Thierry; Peña, O.; Hamon, Jean‐René; Pivan, J. Y.; Moreno, Yanko

doi:10.1016/j.molstruc.2017.05.108

Cited by 7 publications

(7 citation statements)

References 55 publications

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“…The copper(II) coordination polymers (CPs) containing the organic ligands are very attractive due to their application in catalysis, sensor, nonlinear optical, and magnetic materials . Chiral copper(II) CPs are also used as catalysts for asymmetric reactions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Investigations of Chiral NNO Type Copper(II) Coordination Polymers

et al. 2018

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Herein, we report the synthesis and characterizations of chiral copper(II) coordination polymers (CPs) based on Schiff base of (S)‐2‐aminomethylpyrrolidine and salicylaldehyde derivatives. Single crystal X‐ray analysis showed that copper(II) complex is 1D CP, with the repeating units LCu‐OAc (L=ligand) organized in a perpendicular manner, where the copper(II) atoms are six‐coordinated and have a distorted octahedral geometry. Also complex with chlorine counter ion having unusual dimeric structure was synthesized and characterized. It was demonstrated that CPs catalyze the enantioselective Henry reaction with up to 78% ee.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Investigations of Chiral NNO Type Copper(II) Coordination Polymers

et al. 2018

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“…4-stpy and 3-qtpy were prepared as previously reported. 15,19 The 2-stpy ligand has previously been prepared by Srodoba et al, 29 with a 8.5% yield using a procedure based on the two-step Kröhnke methodology. 33 We found that an improved yield of 42.2% of 2-stpy could be obtained by one-pot method under environmentally friendly reaction conditions using PEG and aqueous ammonia as solvents.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…[13][14][15] Along the years, n,2':6',n'' Terpyridines (tpy) as well as all their 4'-substituted derivatives have been subject of intensive structural study, in any of their current forms, viz., n, n'' = 2, the resulting coordination compounds, which includes a wide variety of one-, two-, threedimensional and also discrete supramolecular structures. 14,[16][17][18][19] Although there are several studies on 4'(substituted)-2,2':6',2"-tpy derivatives, 8,9,20,21 to the best of our knowledge, the influence on the photophysical properties of both aryl substituents and the N-position in the terpyridine remains mostly unexplored.…”

Section: Introductionmentioning

confidence: 99%

Influence of structural changes on photophysical properties of terpyridine derivates: Experimental studies and theoretical calculations

Toledo

Brovelli

Soto‐Delgado

et al. 2018

Journal of Molecular Structure

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International audienceFour terpyridine ligands containing different aryl substituents 4'-(4-quinolinyl)-3,2':6′,3″-terpyridine (3-qtpy), 4'-(4-quinolinyl)-2,2':6′,2″-terpyridine (2-qtpy), 4'-(3-methyl-2-thienyl)-4,2':6′,4″-terpyridine (4-stpy) and 4'-(3-methyl-2-thienyl)-2,2':6′,2″-terpyridine (2-stpy) were synthesized in a one-pot procedure and characterized by elemental analysis, FT-IR and 1H- and 13C NMR spectroscopy. Additionally, the 2-stpy structure was confirmed by single crystal X-ray diffraction analysis. The influence of the N-position in the tpy and aryl substituents on the photophysical properties was systematically investigated by spectroscopic methods and simulated by density functional theory (DFT and TD-DFT) calculations. Thermal stability was observed until about 280 °C, making these kind of ligands interesting candidates for their use as complex ligands, which are obtained by solvothermal synthesis under temperatures of about 180 °C. The electrochemical behavior was also investigated. All molecules show irreversible anodic and cathodic voltammetric peaks in organic medium

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“…In [Cu(hfacac) 2 (L 3 )] n •CHCl 3 , the 3,2 :6 ,3"tpy unit adopts conformation A shown in Scheme 1. Moreno has also reported that the reaction of L 1 with [Cu(ttfacac) 2 ] (Httfacac = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3dione) yielded the discrete, trinuclear complex [Cu 3 (ttfacac) 6 (L 1 ) 2 ] [37]. Other relevant 1Dcoordination polymers containing octahedral {Cu(hfacac) 2 (N py ) 2 } building blocks include [Cu(hfacac) 2 (4,4 -bpy)] n (4,4 -bpy = 4,4 -bipyridine) [38] and [Cu(hfacac) 2 (dpss)] n (dpss = di(pyridin-2-yl disulfide) [39] in which the N py donors are trans, and [Cu(hfacac) 2 (bpyb)] n (bpyb = 1,4-bis(pyridin-2-yl)buta-1,3-diyne in which the N py donors are mutually cis [39].…”

Section: Introductionmentioning

confidence: 99%

Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)

et al. 2021

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The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n·2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n·2nC6H5Me, [Cu2(hfacac)4(3)2]n·nC6H4Cl2, [Cu2(hfacac)4(3)2]n·nC6H5Cl, and [Cu(hfacac)2(4)]n·nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2]·H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n·2nC6H4Cl2 and [Cu(hfacac)2(2)]n·2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n·nC6H4Cl2 and [Cu(hfacac)2(4)]n·nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n·nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n·nC6H4Cl2 and [Cu(hfacac)2(4)]n·nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4.

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Unusual trinuclear complex of copper(II) containing a 4′-(3-methyl-2-thienyl)-4,2′:6′,4″-terpyridine ligand. Structural, spectroscopic, electrochemical and magnetic properties

Cited by 7 publications

References 55 publications

Synthesis and Investigations of Chiral NNO Type Copper(II) Coordination Polymers

Synthesis and Investigations of Chiral NNO Type Copper(II) Coordination Polymers

Influence of structural changes on photophysical properties of terpyridine derivates: Experimental studies and theoretical calculations

Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)

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