Design and Synthesis of Luminescent Bis(isocyanoborato) Rhenate(I) Complexes as a Selective Sensor for Cyanide Anion

Xiao, Yelan; Chu, Wing‐Kin; Ng, Chi-On; Cheng, Shun‐Cheung; Tse, Man‐Kit; Yiu, Shek‐Man; Ko, Chi‐Chiu

doi:10.1021/acs.organomet.0c00204

Cited by 16 publications

(14 citation statements)

References 53 publications

(44 reference statements)

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“…As noted above, many prior investigations of cyanoborylated complexes have focused on 5d metals, [55][56][57][58][59]61,64 where the ligand field splitting is inherently larger than in 4d metals and thermal population of the 3 MC from the 3 MLCT state is therefore less important. Thus, it is not too surprising that the effect illustrated by Figure 6 has been unnoticed until now.…”

Section: Uv−vis Absorption and Luminescence Propertiesmentioning

confidence: 99%

“…Important prior work on isocyanoborato complexes focused on 5d metals including Ir(III), Re(I), − and Os(II) as well as on Ni(II), Pd(II), Pt(II), Cu(I), , and Ag(I) . Very recently, Ru(II) and Fe(II) isocyanoborato complexes were studied in the context of electrochemistry and spectroscopy, but their photoreactivity and photochemistry have not yet been reported. − Attachment of B(C 6 F 5 ) moieties to the cyanide ligands of heteroleptic complexes with α-diimine chelates usually results in the stabilization of the metal-centered d orbitals, whereas the diimine π* orbitals are less affected .…”

mentioning

confidence: 99%

“…Very recently, Ru(II) and Fe(II) isocyanoborato complexes were studied in the context of electrochemistry and spectroscopy, but their photoreactivity and photochemistry have not yet been reported. − Attachment of B(C 6 F 5 ) moieties to the cyanide ligands of heteroleptic complexes with α-diimine chelates usually results in the stabilization of the metal-centered d orbitals, whereas the diimine π* orbitals are less affected . This leads to a blue-shift of the metal-to-ligand charge-transfer (MLCT) absorption and emission features and a concomitant increase in 3 MLCT energy. − The photostability of our new Ru(II) compounds and their broad applicability to photocatalysis is largely attributable to this effect.…”

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confidence: 99%

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Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis

Schmid

Kerzig

Prescimone

et al. 2021

JACS Au

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Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic ruthenium(II) cyanide complexes with α-diimine ancillary ligands is identified as a useful concept to elevate the energies of photoactive metal-to-ligand charge-transfer (MLCT) states and to obtain unusually photorobust compounds suitable for thermodynamically challenging energy transfer catalysis as well as oxidative and reductive photoredox catalysis. B(C 6 F 5 ) 3 groups attached to the CN – ligands stabilize the metal-based t 2g -like orbitals by ∼0.8 eV, leading to high 3 MLCT energies (up to 2.50 eV) that are more typical for cyclometalated iridium(III) complexes. Through variation of their α-diimine ligands, nonradiative excited-state relaxation pathways involving higher-lying metal-centered states can be controlled, and their luminescence quantum yields and MLCT lifetimes can be optimized. These combined properties make the respective isocyanoborato complexes amenable to photochemical reactions for which common ruthenium(II)-based sensitizers are unsuited, due to a lack of sufficient triplet energy or excited-state redox power. Specifically, this includes photoisomerization reactions, sensitization of nickel-catalyzed cross-couplings, pinacol couplings, and oxidative decarboxylative C–C couplings. Our work is relevant in the greater context of tailoring photoactive coordination compounds to current challenges in synthetic photochemistry and solar energy conversion.

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Section: Uv−vis Absorption and Luminescence Propertiesmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis

Schmid

Kerzig

Prescimone

et al. 2021

JACS Au

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“…42,43 Of interest is that BCF/BPh3 adducts of heteroleptic Re(I) diimine carbonyls have shown promise as selective sensors for cyanide anion. 44 Most recently, Wenger et al have boronated heteroleptic Ru(II) and Ir(III) diimine complexes and demonstrated their high activity for energy transfer and photoredox catalysis. 45,46 Studies of cyanometallates have been driven by the promise of applications in magnetic materials involving single-molecule/Prussian-Blue analogues and in electrode materials for solid-state batteries.…”

Section: N-methylpyrrolidinonementioning

confidence: 99%

Boronated Cyanometallates

McNicholas,

Nie,

Jose

et al. 2022

Preprint

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Fourteen boronated cyanometallates ([M(CN-BR3)6]3/4/5– (M = Cr, Mn, Fe, Ru, Os, R = BPh3, B(2,4,6,-F3C6H2)3, B(C6F5)3) have been characterized by X-ray crystallography and spectroscopy [UV-vis-NIR, NMR, IR, spectroelectrochemistry, and magnetic circular dichroism (MCD)]; CASSCF+NEVPT2 methods were employed in calculations of electronic structures. For (t2g)5 electronic configurations, the lowest energy ligand-to-metal charge transfer (LMCT) absorptions and MCD C terms in the spectra of boronated species have been assigned to transitions from cyanide σ+π + B-C borane σ orbitals. CASSCF+NEVPT2 calculations including t1u and t2u orbitals reproduced t1u/t2u → t2g excitation energies. All ([M(CN-BR3)6]3/4− complexes exhibited highly electrochemically reversible redox couples. Notably, the formal potentials of all five [M(CN-B(C6F5)3)6]3− anions scale with LMCT energies; and Mn(I) and Cr(II) compounds, (K(18-crown-6))5[Mn(CN-B(C6F5)3)6] and (TBA)4[Cr(CN-B(C6F5)3)6], are surprisingly stable. Continuous wave and pulsed electron paramagnetic resonance (hyperfine sublevel correlation) spectra were collected for all Cr(III) complexes; as expected, 14N hyperfine splittings are greater for (TBA)3[Cr(NC-BPh3)6] than for (TBA)3[Cr(CN-BPh3)6]. Using (TBA)4[Fe(CN-B(C6F5)3)6] and (TBA)3[Fe(CN)6], a model flow battery was constructed and found to have an 80% energy effi-ciency.

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“…Currently, anion sensors have been the subject of considerable interest for their numerous roles in various processes in the fields of biology, catalysis, industry, and environmental protection. Anion sensors have also been used in devices such as television screens, as well as in monitoring and microelectronic sensors [1][2][3][4][5]. Researchers are interested in anion sensors with different dimensional structures, such as 2-and 3-dimensional patterns on carbon nanotubes and MOF structures [6,7].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure and Optical Properties of 2-(3-(Hexyloxy)-5-Methylphenoxy)-N-(4-Nitrophenyl)acetamide for Anion Detection

et al. 2021

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In this study, 2-(3-(hexyloxy)-5-methylphenoxy)-N-(4-nitrophenyl)acetamide (sensor L1) was synthesized and characterized by FT–IR, ESI–MS, 1H and 13C NMR spectroscopy, elemental analysis, and single crystal X-ray techniques. The crystal structure and space group of sensor L1 was monoclinic and P21, respectively. The crystal packing of sensor L1 was dominantly linked by two strong hydrogen bonds forming a six membered ring pattern. The binding properties of sensor L1 and various anions (F−, Cl−, Br−, CH3COO−, C6H5COO−, and H2PO4−) were investigated by UV–Vis and 1H NMR spectroscopy in DMSO. The proton resonance signals of sensor L1 and F− greatly changed positions when compared to those of anions. The solution color of sensor L1 changed from pale yellow to orange in the presence of F−. The UV–Vis results indicate that sensor L1 and F− ions underwent an internal charge transfer process. The stoichiometric complex was confirmed by Job’s method, revealing a 1:1 formation for sensor L1 and fluoride. Our results show that sensor L1 is highly selective for fluoride ions over other anions.

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Design and Synthesis of Luminescent Bis(isocyanoborato) Rhenate(I) Complexes as a Selective Sensor for Cyanide Anion

Cited by 16 publications

References 53 publications

Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis

Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis

Boronated Cyanometallates

Synthesis, Crystal Structure and Optical Properties of 2-(3-(Hexyloxy)-5-Methylphenoxy)-N-(4-Nitrophenyl)acetamide for Anion Detection

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