Green to Red Luminescence Switchable by Excitation Light in Cyanido-Bridged Tb<sup>III</sup>–W<sup>V</sup> Ferromagnet

Chorąży, Szymon; Nakabayashi, Koji; Ohkoshi, Shin‐ichi; Sieklucka, Barbara

doi:10.1021/cm501954e

Cited by 59 publications

(76 citation statements)

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“…It enables the observation of visible and NIR photoluminescence of accompanying emissive chromophores [32]. In effect, a considerable number of photoluminescent d–f coordination networks based on octacyanidometallates were reported (Figure 7 and Figure 8, Table 4) [101,102,103,104,105,106,107,108,109,110]. In the aqueous solution, trivalent lanthanide(3+) and [M V (CN) 8 ] 3− ions produce the cyanido-bridged [Ln III (H 2 O) 5 ][M V (CN) 8 ] (Ln = Sm, Eu, Gd, Tb; M = Mo, W) layered frameworks of a square grid topology [101,102,103].…”

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

“…The rich scope of diverse lanthanides(3+) photoluminescence, and their interaction with organic 2,2’-bis(2-oxazoline) (box) organic chromophore was beautifully presented in the cyanido-bridged [Ln III (box) n (dmf) m ][M V (CN) 8 ]· x (solvent) (Ln = Ce–Dy, n = 2, m = 2; Ln = Ho–Yb, n = 1, m = 3; M = Mo, W) layers of a mixed 4- and 8-membered metal rings topology, showing the unusual sliding of coordination layers depending on lanthanides [109,110]. The TbW derivative, named [Tb III (box) 2 (dmf) 2 ][W V (CN) 8 ]·H 2 O (Figure 8a), reveals the excitation-dependent visible luminescence switchable between Tb 3+ green emission induced under the deep UV excitation of the interconfigurational d-f transition of the 4f-metal centre, and red box-based phosphorescence detected for the UV excitation around 340 nm that directs the energy mainly towards the ligand excited states (Figure 8b) [109].…”

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

“…The TbW derivative, named [Tb III (box) 2 (dmf) 2 ][W V (CN) 8 ]·H 2 O (Figure 8a), reveals the excitation-dependent visible luminescence switchable between Tb 3+ green emission induced under the deep UV excitation of the interconfigurational d-f transition of the 4f-metal centre, and red box-based phosphorescence detected for the UV excitation around 340 nm that directs the energy mainly towards the ligand excited states (Figure 8b) [109]. Similar effect was found for the analogous TbMo system while the other members of the LnMo family showed lanthanide-dependent visible and/or NIR emission.…”

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

“…Crystal structure and optical properties of two-dimensional [Tb III (box) 2 (dmf) 2 ] [W V (CN) 8 ]·H 2 O (box = 2,2’-bis(2-oxazoline)) coordination polymers: ( a ) the views of the single cyanido-bridged layer, and the arrangement of layers, ( b ) the excitation-dependent emission spectra collected at T = 77 K. Colours for the structural diagram: Tb, red; W, dark blue; CN − , blue; box, orange; dmf, grey [109]. …”

Section: Figurementioning

confidence: 99%

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Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

2017

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Solid-state functional luminescent materials arouse an enormous scientific interest due to their diverse applications in lighting, display devices, photonics, optical communication, low energy scintillation, optical storage, light conversion, or photovoltaics. Among all types of solid luminophors, the emissive coordination polymers, especially those based on luminescent trivalent lanthanide ions, exhibit a particularly large scope of light-emitting functionalities, fruitfully investigated in the aspects of chemical sensing, display devices, and bioimaging. Here, we present the complete overview of one of the promising families of photoluminescent coordination compounds, that are heterometallic d–f cyanido-bridged networks composed of lanthanide(3+) ions connected through cyanide bridges with polycyanidometallates of d-block metal ions. We are showing that the combination of cationic lanthanide complexes of selected inorganic and organic ligands with anionic homoligand [M(CN)x]n− (x = 2, 4, 6 and 8) or heteroligand [M(L)(CN)4]2− (L = bidentate organic ligand, M = transition metal ions) anions is the efficient route towards the emissive coordination networks revealing important optical properties, including 4f-metal-centred visible and near-infrared emission sensitized through metal-to-metal and/or ligand-to-metal energy transfer processes, and multi-coloured photoluminescence switchable by external stimuli such as excitation wavelength, temperature, or pressure.

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Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

Section: Octacyanidometallates [Miv/v(cn)8]4−/3− (M = Mo W)mentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

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Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

2017

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“…Namely, most of the transition metal ions are not emissive due to 25 the nonradiative relaxation through interactions with low-lying excited states, that makes synthesis of emissive magnets very difficult. [15,16] Besides progress in chemical synthesis, a better understanding of structural and magnetic correlations is achieved due to the progress in experimental techniques in physics. Electron spin or paramagnetic resonance (ESR or EPR) 30 spectroscopy provides insights into local properties of paramagnetic centers and microscopic picture of the interactions.…”

Section: Introductionmentioning

confidence: 99%

3D oxalate-based coordination polymers: Relationship between structure, magnetism and color, studied by high-field ESR spectroscopy

et al. 2017

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The detailed high field electron spin resonance (HF-ESR) study of three 3D oxalate-based coordination polymers with antiferromagnetic ordering below 13 K, supported by crystallographic, photoluminescence (PL), elemental (EDX) and X-band ESR analysis, is presented. Two of the investigated compounds gives rise to slightly different g-factors, is discussed with respect to the different colors of these compounds.

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Fe^II Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe₉[Re(CN)₈]₆} Spherical Cluster

et al. 2015

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The self-assembly of iron(II) ions with rare octacyanidorhenate(V) metalloligands in a methanolic solution results in the formation of a nanometric pentadecanuclear {Fe II 9 [Re V (CN) 8 ] 6 (MeOH) 24 }·10 MeOH (1) molecule with a six-capped body-centered cubic topology. The cluster demonstrates a thermally-induced spin-crossover phase transition at T 1/2 = 195 K which occurs selectively for a single Fe II ion embedded in the center of a cluster core.Molecule-based magnets, built of magnetically active metal complexes or organic radicals, have been intensively studied because of various magnetic properties, including magnetic ordering below the critical temperature (T c ), [1][2][3] spin-transition phenomena, [4][5][6] and slow magnetic relaxation. [7][8][9] Significant interest has been focused on cyanido-bridged bimetallic assemblies which exhibit magnetic coupling of a predictable strength, giving magnetic ordering at various T c values, in some cases up to 100 8C. [10][11][12] These systems were found to efficiently combine magnetism with other functionalities, such as ferroelectricity, [13] chirality, [14][15][16][17] luminescence, [18] sensitivity to guest molecules, [19][20][21] zero thermal expansion, [22] or photoinduced phase transitions. [24][25][26] The interaction between this additional property and magnetism gives rise to extra cross-effects. [27][28][29][30] We have shown magnetic second harmonic generation (MSHG), [31,32] light-induced spin-crossover magnetism, [23] and a 908 switching of the SHG polarization plane when chirality was coupled with photomagnetism. [14] Magnetic materials based on polynuclear clusters have attracted particular attention as they can show a high-spin ground state leading to single-molecule magnetism (SMM) [33] or to a magnetocaloric effect. [34] Among such materials, bimetallic [M(CN) 8 ]-based clusters have great potential, [35] as demonstrated by a family of {M 9 M' 6 } pentadecanuclear clusters {M II 9 [M' V (CN) 8 ] 6 (MeOH) 24 } (M= 3d metal; M ' = Mo, W; MeOH = methanol) which show a diverse range of magnetic functionalities, including high spin, [36][37][38] SMM, [39,40] and thermally induced charge transfer. [41,42] In this regard, the application of the spin-crossover (SCO) effect to polynuclear molecules is rare. SCO was broadly investigated for mononuclear complexes, based mainly on the Fe II ion, [43,44] and coordination polymers offering efficient intramolecular interactions giving thermal hysteresis loops, crucial for applications such as memory devices. [45,46] Apart from a number of di-and tetranuclear species which demonstrate a spectacular multistep SCO effect, [47][48][49][50] there are only three well-characterized examples of larger SCO clusters: a) pentanuclear {[Fe II (tmphen) 2 ] 3 [M III (CN) 6 ] 2 } (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline; M = Fe, Co), [51] b) heptanuclear {[Fe III (salpet)] 6 [Fe II (CN) 6 ]}Cl 2 (salpet = a pendadentate Schiff base), [52] and c) tetradecanuclear {Fe II 6 [Cu I (Tp 4Àpy )] 8 } 4+ (Tp 4-py = tris{3-...

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Green to Red Luminescence Switchable by Excitation Light in Cyanido-Bridged Tb^III–W^V Ferromagnet

Cited by 59 publications

References 34 publications

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

3D oxalate-based coordination polymers: Relationship between structure, magnetism and color, studied by high-field ESR spectroscopy

Fe^II Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe₉[Re(CN)₈]₆} Spherical Cluster

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Green to Red Luminescence Switchable by Excitation Light in Cyanido-Bridged TbIII–WV Ferromagnet

Cited by 59 publications

References 34 publications

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

3D oxalate-based coordination polymers: Relationship between structure, magnetism and color, studied by high-field ESR spectroscopy

FeII Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe9[Re(CN)8]6} Spherical Cluster

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Green to Red Luminescence Switchable by Excitation Light in Cyanido-Bridged Tb^III–W^V Ferromagnet

Fe^II Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe₉[Re(CN)₈]₆} Spherical Cluster