Fluorescent Naphthalene Diols as Bridging Ligands in LnIII Cluster Chemistry: Synthetic, Structural, Magnetic, and Photophysical Characterization of LnIII8 “Christmas Stars”

Alexandropoulos, Dimitris I.; Fournet, Adeline; Cunha-Silva, Luı́s; Mowson, Andrew M.; Bekiari, Vlasoula; Christou, George; Stamatatos, Theocharis C.

doi:10.1021/ic500806n

Cited by 40 publications

(23 citation statements)

References 23 publications

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“…Solid-state, room temperature emission spectra upon CW laser excitation at 405 nm in the visible ( Figure S18) and near-IR ( Figure 12 All these experimental facts indicate that the broad green emission at ~525 to 540 nm in the spectra of all the eight complexes is salanHcentered and, thus, the coordinated ligand cannot act as a "sensitizer" for 4f-metal luminescence. It seems that this Ln III -independent emission is due to an efficient Ln III -to-salanH back energy transfer [50,52,83]. A reason for this behavior might be the fact that the main absorption bands of coordinated salanH (at ~500 nm) are not close to the region where some Ln III ions absorb (<400 nm) [57].…”

Section: Emission Studiesmentioning

confidence: 99%

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

et al. 2018

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The reactions of hydrated lanthanide(III) [Ln(III)] nitrates and salicylideneaniline (salanH) have provided access to two families of mononuclear complexes depending on the reaction solvent used. In MeCN, the products are [Ln(NO3)3(salanH)2(H2O)]·MeCN, and, in MeOH, the products are [Ln(NO3)3(salanH)2(MeOH)]·(salanH). The complexes within each family are proven to be isomorphous. The structures of complexes [Ln(NO3)3(salanH)2(H2O)]·MeCN (Ln = Eu, 4·MeCN_Eu, Ln = Dy, 7·MeCN_Dy; Ln = Yb, 10·MeCN_Yb) and [Ln(NO3)3(salanH)2(MeOH)]·(salanH) (Ln = Tb, 17_Tb; Ln = Dy, 18_Dy) have been solved by single-crystal X-ray crystallography. In the five complexes, the LnIII center is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms from the two monodentate zwitterionic salanH ligands, and one oxygen atom from the coordinated H2O or MeOH group. The salanH ligands are mutually “cis” in 4·MeCN_Eu, 7·MeCN_Dy and 10·MeCN_Yb while they are “trans” in 17_Tb and 18_Dy. The lattice salanH molecule in 17_Tb and 18_Dy is also in its zwitterionic form with the acidic H atom being clearly located on the imine nitrogen atom. The coordination polyhedra defined by the nine oxygen donor atoms can be described as spherical tricapped trigonal prisms in 4·MeCN_Eu, 7·MeCN_Dy, and 10·MeCN_Yb and as spherical capped square antiprisms in 17_Tb and 18_Dy. Various intermolecular interactions build the crystal structures, which are completely different in the members of the two families. Solid-state IR data of the complexes are discussed in terms of their structural features. 1H NMR data for the diamagnetic Y(III) complexes provide strong evidence that the compounds decompose in DMSO by releasing the coordinated salanH ligands. The solid complexes emit green light upon excitation at 360 nm (room temperature) or 405 nm (room temperature). The emission is ligand-based. The solid Pr(III), Nd(III), Sm(III), Er(III), and Yb(III) complexes of both families exhibit LnIII-centered emission in the near-IR region of the electromagnetic spectrum, but there is probably no efficient salanH→LnIII energy transfer responsible for this emission. Detailed magnetic studies reveal that complexes 7·MeCN_Dy, 17_Tb and 18_Dy show field-induced slow magnetic relaxation while complex [Tb(NO3)3(salanH)2(H2O)]·MeCN (6·MeCN_Tb) does not display such properties. The values of the effective energy barrier for magnetization reversal are 13.1 cm−1 for 7·MeCN_Dy, 14.8 cm−1 for 17_Tb, and 31.0 cm−1 for 18_Dy. The enhanced/improved properties of 17_Tb and 18_Dy, compared to those of 6_Tb and 7_Dy, have been correlated with the different supramolecular structural features of the two families. The molecules [Ln(NO3)3(salanH)2(MeOH)] of complexes 17_Tb and 18_Dy are by far better isolated (allowing for better slow magnetic relaxation properties) than the molecules [Ln(NO3)3(salanH)2(H2O)] in 6·MeCN_Tb and 7·MeCN_Dy. The perspectives of the present initial studies in the Ln(III)/salanH chemistry are discussed.

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Section: Emission Studiesmentioning

confidence: 99%

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

et al. 2018

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“…In recent years, 3d-4f polynuclear Coordination Clusters (CCs) have attracted increasing interest as a result of their extraordinary and fascinating structural characteristics [1][2][3][4][5] as well as their many potential applications in fields such as molecular magnetism, [6][7][8] optical materials [9][10][11][12][13] and catalysis. [14][15][16][17][18] In particular, the first heteronuclear Zn II -Eu III /Sm III CCs were reported in 1995 by Brennan et al 19,20 ;…”

Section: Introductionmentioning

confidence: 99%

Four New Families of Polynuclear Zn-Ln Coordination Clusters. Synthetic, Topological, Magnetic, and Luminescent Aspects

Griffiths

Mayans

Shipman

et al. 2017

Crystal Growth & Design

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12) with robust and novel topologies. Synthetic aspects are discussed. A comprehensive topological analysis of all reported Zn II /Ln III CCs with a core nuclearity of four and above is presented and identifies that families (4-6) and (7-9) are the first examples of the 2,3,4M6-1 motif in Zn II /Ln III chemistry. Magnetic studies are presented for the Dy III analogues (1, 7 and 10) are presented, 7 demonstrates field-induced slow relaxation of the magnetization. Fluorescence studies are also discussed.

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“…It is noteworthy that, nowadays, most of the reported lanthanide‐based molecular nanomagnets are based on diamagnetic ligands, such as Schiff bases, aminopolyalcohols,, and oximes,, while paramagnetic ligands such as nitronyl nitroxide radicals to construct such compounds are barely used , , . Nitronyl nitroxide radicals as spin carriers are appealing building blocks to construct molecular magnetic materials owing to the advantage of their effective exchange interaction as well as stability , .…”

Section: Introductionmentioning

confidence: 99%

Construction and Magnetic Study of One‐Dimensional Lanthanide–Radical Chains Involving Pyridinone‐Substituted Nitronyl Nitroxide Radicals

Guo

Sun

et al. 2018

Eur J Inorg Chem

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A new nitronyl nitroxide radical-containing pyridinone group (NIT-PhPyO, 1) has been synthesized {NIT-PhPyO = 2-[4-(4-pyridinone)phenyl]-4,4,5,5-tetramethylimidazoline-1oxyl-3-oxide}. By using this functionlized nitronyl nitroxide, two isomorphic lanthanide-nitronyl nitroxide radical compounds [{Ln(hfac) 3 } 3 (NIT-PhPyO) 2 ] n (Ln = Gd 2 and Dy 3; hfac = hexafluoroacetylacetonate) have been successfully obtained. X-ray spectroscopic analysis reveals that complexes 2 and 3 possess [a] Supporting Information (see footnote on the first page of this article): Selected bond lengths and angles for 1-3, SHAPE analysis for 3, molecular structure of complex 3, the coordination polyhedron of all Dy III ions in 3, the 1D chain of 3, packing of the chains for complex 3, and the additional magnetic data for 3.

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Fluorescent Naphthalene Diols as Bridging Ligands in Ln^III Cluster Chemistry: Synthetic, Structural, Magnetic, and Photophysical Characterization of Ln^III₈ “Christmas Stars”

Abstract: The initial employment of the fluorescent bridging ligand naphthalene-2,3-diol in 4f-metal coordination chemistry has provided access to a new family of Ln(III)8 clusters with a "Christmas-star" topology, single-molecule magnetism behavior, and ligand-centered emissions.

Cited by 40 publications

References 23 publications

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

Mononuclear Lanthanide(III)-Salicylideneaniline Complexes: Synthetic, Structural, Spectroscopic, and Magnetic Studies

Four New Families of Polynuclear Zn-Ln Coordination Clusters. Synthetic, Topological, Magnetic, and Luminescent Aspects

Construction and Magnetic Study of One‐Dimensional Lanthanide–Radical Chains Involving Pyridinone‐Substituted Nitronyl Nitroxide Radicals

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