Polycations Stabilised by Borosulfates: [Au3Cl4][B(S2O7)2] and the One‐Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)

Sutorius, Stefan; Gerven, David van; Olthof, Selina; Rasche, Bertold; Bruns, Jörn

doi:10.1002/chem.202200004

“…[ 35 , 36 , 37 ] and even more recently we reported on two highly untypical heteropoly Au−Cl cations stabilized by [B(S 2 O 7 ) 2 ] 2 − anions. [38] …”

Section: Resultsmentioning

confidence: 99%

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Gerven

¹

,

Sutorius

²

,

Bruns

³

et al. 2022

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The reaction of elemental iodine and SO 3 in a sealed glass ampoule yielded a turquoise‐colored solution. At temperatures below 7 °C, deep red crystals of (I 4 )[S 6 O 19 ] grow. With the addition of B 2 O 3 and pyridine‐SO 3 complex red crystals of (I 4 )[B(S 2 O 7 ) 2 ] 2 can be obtained after heating the mixture to 120 °C. The combination of an (I 4 ) 2+ cation with oxoanions has previously not been observed. Both anions have a significant but different influence on the structural properties of the (I 4 ) 2+ cation.

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Photolumineszenz von Mn²⁺ in dem Borosulfat Zn[B₂(SO₄)₄] : Mn²⁺ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Träger,

Pasqualini,

Huppertz

et al. 2023

Angewandte Chemie

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The impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in e.g., phosphor‐converted white light‐emitting diodes (pc‐wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5‐3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal‐ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer‐like borosulfate ligand in the Mn(II)‐containing solid solutions Zn1‐xMnx[B2(SO4)4] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2(SO4)4]:Mn2+ shows orange narrow‐band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn‐O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal‐ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.

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Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

Träger,

Pasqualini,

Huppertz

et al. 2023

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The impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in e.g., phosphor‐converted white light‐emitting diodes (pc‐wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5‐3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal‐ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer‐like borosulfate ligand in the Mn(II)‐containing solid solutions Zn1‐xMnx[B2(SO4)4] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2(SO4)4]:Mn2+ shows orange narrow‐band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn‐O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal‐ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.

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Polycations Stabilised by Borosulfates: [Au₃Cl₄][B(S₂O₇)₂] and the One‐Dimensional Metal [Au₂Cl₄][B(S₂O₇)₂](SO₃)

Cited by 5 publications

References 51 publications

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Photolumineszenz von Mn²⁺ in dem Borosulfat Zn[B₂(SO₄)₄] : Mn²⁺ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands

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Polycations Stabilised by Borosulfates: [Au3Cl4][B(S2O7)2] and the One‐Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)

Cited by 5 publications

References 51 publications

Stabilizing the Homopolycation (I4)2+ with a Hexasulfate in (I4)[S6O19] and a Borosulfate in (I4)[B(S2O7)2]2

Stabilizing the Homopolycation (I4)2+ with a Hexasulfate in (I4)[S6O19] and a Borosulfate in (I4)[B(S2O7)2]2

Photolumineszenz von Mn2+ in dem Borosulfat Zn[B2(SO4)4] : Mn2+ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands

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Polycations Stabilised by Borosulfates: [Au₃Cl₄][B(S₂O₇)₂] and the One‐Dimensional Metal [Au₂Cl₄][B(S₂O₇)₂](SO₃)

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Stabilizing the Homopolycation (I₄)²⁺ with a Hexasulfate in (I₄)[S₆O₁₉] and a Borosulfate in (I₄)[B(S₂O₇)₂]₂

Photolumineszenz von Mn²⁺ in dem Borosulfat Zn[B₂(SO₄)₄] : Mn²⁺ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden

Photoluminescence of Mn²⁺ in the Borosulfate Zn[B₂(SO₄)₄] : Mn²⁺—A Tool to Detect Weak Coordination Behavior of Ligands