The incorporation of photochromic moieties into coordination polymers is of particular interest because it can endow them with various switching functions such as electrical conductivity, luminescence, and magnetism. In this context, a viologen ligand as a photochromic moiety was incorporated into 3d-4f heterobimetallic hexacyanoferrates, resulting in three novel 3-D photochromic complexes with different metal cations, namely {[Ln(BCEbpy) M(CN) (HO)]·2HO} (denoted as CoDy, CoEu, and FeDy, Ln = Dy, Eu; M = Fe, Co, HBCEbpy·2Br = N,N'-bis(carboxymethyl)-4,4'-bipyridinium dibromide). And the photoresponsive mechanism has been well discussed based on the solid UV-vis, IR, ESR, photoluminescence, and magnetism data. Moreover, accompanying the photochromic process, these unique complexes exhibit different photomagnetic behaviors upon UV-vis irradiation at RT because of the different ferromagnetic coupling interactions between photogenerated radicals and lanthanide cations.
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http://dx.doi.org/10.1039/d0dt04358c | DOI Listing |
Dalton Trans
December 2024
Dipartimento Scienze Chimiche, Università degli Studi di Catania, and INSTM UdR Catania, Viale Andrea Doria 6, 95125 Catania, Italy.
This work reports the engineering and functional properties of an emerging class of heterobimetallic 3d-4f ionic complexes designed with cobalt and rare-earth (RE) metals. We present a comprehensive examination of the structural, magnetic, optical, and thermal properties of the heterobimetallic ionic complexes with the general formula [Co(hfa)][RE(hfa)tetraglyme] (RE = Dy, Eu, and Y), where the metal centres are coordinated by hexafluoroacetylacetonate (Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), β-diketone and tetraglyme (2,5,8,11,14-pentaoxapentadecane) polyether. Structural analysis reveals an octahedral coordination geometry enveloping the cobalt(II) centre, characterized by inherent symmetry properties consistent across the derivatives, while a capped square-antiprism coordination polyhedron is observed for the RE ions.
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June 2024
Department of Chemistry, King's College London, Britannia House, 7 Trinity Street, London, SE1 1DB, UK.
Complexes featuring multiple metal centres are of growing interest regarding metal-metal cooperation and its tuneability. Here the synthesis and characterisation of heterobimetallic complexes of a 3d metal (4: Mn, 5: Co) and lanthanum supported by a (1,1,1-tris[(3-methoxysalicylideneamino)methyl]ethane) ligand is reported, as well as discussion of their electronic structure electron paramagnetic resonance (EPR) spectroscopy, electrochemical experiments and computational studies. Competitive binding experiments of the ligand and various metal salts unequivocally demonstrate that in these heterobimetallic complexes the 3d metal (Mn, Co) selectively occupies the κ-NO binding site of the ligand, whilst La occupies the κ-O metal binding site in line with their relative oxophilicities.
View Article and Find Full Text PDFActa Crystallogr C Struct Chem
February 2024
Institute of High Energy Physics Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
Dalton Trans
November 2022
Institut des Sciences Chimiques de Rennes UMR 6226 CNRS-UR1, Université de Rennes 1, 35042 Rennes Cedex, France.
The reaction between the 2-(1-(2,6-di(pyrazol-1-yl)-4-methylpyridyl)-4,5-(4,5-bis(propylthio)-tetrathiafulvalenyl)-1-benzimidazol-2-yl)-pyridine ligand (L), 1 equivalent of Ln(hfac)·2HO/Dy(tta)·2HO (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate, tta = 2-thenoyltrifluoroacetonate) and M(hfac)·2HO leads to the formation of heteroleptic 3d-4f dinuclear complexes of formula [MLn(hfac)(L)] (M(II) = Cd, Zn, Co, Mn, Ni and Ln(III) = Dy, Yb, Nd) and [ZnDy(tta)(hfac)(L)]·(CHCl). Their X-ray structures reveal that the two coordination sites are occupied by one Ln(III) ion and one M(II) transition metal respectively. The M(II) ions are coordinated to the benzoimidazolylpyridine (bzip) moiety in a NO coordination sphere, while the Ln(III) ions are coordinated to the 2,6-di(pyrazol-1-yl)-4-pyridine (dpp) moiety in a NO surrounding.
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October 2021
Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, CZ-771 46 Olomouc, Czech Republic.
A series of heterobimetallic Ln-V compounds [Ln(VO)L(NO)(HO)] (Ln = Gd(1), Tb(2), Dy(3), and Er(4)) assembled by a Schiff base ligand (HL = ,'-bis(1-hydroxy-2-benzylidene-6-methoxy)-1,7-diamino-4-azaheptane) were prepared and studied with experimental and theoretical methods. The single-crystal X-ray analysis revealed the change of the coordination number from 10 found in 1-3 to 9 confirmed in 4. The DC magnetic data were fit with several Hamiltonians to extract the exchange and anisotropy parameters of complexes 1-4.
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