Directional Energy Transfer in Nanocrystals of [Ru(2,2′‐bipyridine)<sub>3</sub>]­[NaCr(oxalate)<sub>3</sub>]

Previtera, Elia; Tissot, Antoine; Hauser, Andreas

doi:10.1002/ejic.201501204

Cited by 7 publications

(10 citation statements)

References 63 publications

(24 reference statements)

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“…This accounts for the observed shorter lifetimes and supports our assumption of a distance‐dependent doublet‐doublet energy transfer between the chromium(III) centers in the crystals. Energy migration between chromium(III) complexes has been observed in solution and in the solid state before [14g,25] . For example, in Na[Ru(bpy) 3 ][Cr(ox) 3 ] (bpy=2,2’‐bipyridine, ox 2− =oxalate 2− ), the excitation energy is transferred from excited [Cr(ox) 3 ] 3− moieties in the bulk to ground state molecules near the microcrystal surface [25] .…”

Section: Resultsmentioning

confidence: 99%

Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

et al. 2022

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The molecular ruby analogue [Cr(ddpd)2]3+ (ddpd=N,N’‐dimethyl‐N,N’‐dipyridine‐2‐ylpyridine‐2,6‐diamine) exhibits near infrared (NIR) emission with a high photoluminescence (PL) quantum yield ΦPL of 11 % and a lifetime of 898 μs in deaerated water at room temperature. While ligand‐based control of the photophysical properties has received much attention, influences of the counter anions and microenvironment are still underexplored. In this study, the luminescence properties of the molecular ruby were systematically examined for the counter anions Cl−, Br−, [BF4]−, [PF6]−, [BPh4]−, and [BArF24]− in acetonitrile (MeCN) solution, in crystals, and embedded into polystyrene nanoparticles (PSNP). Stern‐Volmer analyses of the oxygen quenching studies in the intensity and lifetime domain showed the highest oxygen sensitivity of the complexes with the counter anions of [BF4]− and [BArF24]−, which also revealed the longest luminescence lifetimes. Embedding [Cr(ddpd)2][PF6]3 in PSNPs and shielding with poly(vinyl alcohol) yields a strongly NIR‐emissive oxygen‐insensitive material with a record ΦPL of 15.2 % under ambient conditions.

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Section: Resultsmentioning

confidence: 99%

Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

et al. 2022

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Section: Resultsmentioning

confidence: 99%

“…[78] The finding that the 4 LMCT configurations can feed the emissive 2 T 1 4 A 2 / 2 E 4 A 2 excited state of 1 and 2 (see excitation spectra discussed below) suggests that these complexes may also be interesting to investigate as sensitizers based on earth-abundant metal ions [79,80] or as acceptors in supramolecular architectures. [81][82][83][84] The visible region of the spectrum of 1 reveals a shoulder on the low-energy tail of the LMCT-related band at ~417 nm and a well-defined absorption band peaking at around 571 nm (ɛ = 414 M À 1 cm À 1 ). These two features are tentatively assigned to the spin-allowed 4 A 2 !…”

Section: Spectroscopic and Photophysical Propertiesmentioning

confidence: 99%

Synthesis and Characterisation of Luminescent [Cr^III₂L(μ‐carboxylato)]³⁺ Complexes with High‐Spin S=3 Ground States (L=N₆S₂ donor ligand)

Börner

Klose

Suburu

et al. 2021

Chemistry A European J

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The synthesis, structure, magnetic, and photophysical properties of two dinuclear, luminescent, mixedligand [Cr III 2 L(O 2 CR)] 3 + complexes (R = CH 3 (1), Ph (2)) of a 24membered binucleating hexa-aza-dithiophenolate macrocycle (L) 2À are presented. X-ray crystallographic analysis reveals an edge-sharing bioctahedral N 3 Cr(μ-SR) 2 (μ 1,3 -O 2 CR)CrN 3 core structure with μ 1,3 -bridging carboxylate groups. A ferromagnetic superexchange interaction between the electron spins of the Cr 3 + ions leads to a high-spin (S = 3) ground state. The coupling constants (J = + 24.2(1) cm À 1 (1), + 34.8(4) cm À 1 (2), H = À 2JS 1 S 2 ) are significantly larger than in related bis-μalkoxido-μ-carboxylato structures. DFT calculations performed on both complexes reproduce both the sign and strength of the exchange interactions found experimentally. Frozen methanol-dichloromethane 1 : 1 solutions of 1 and 2 luminesce at 750 nm when excited into the 4 LMCT state on the 4 A 2 ! 2 T 1 (ν 2 ) bands (λ exc = 405 nm). The absolute quantum yields (Φ L ) for 1 and 2 were found to be strongly temperature dependent. At 77 K in frozen MeOH/CH 2 Cl 2 glasses, Φ L = 0.44 � 0.02 (for 1), Φ L = 0.45 � 0.02 (for 2).

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“…Photoredox catalytic cycloadditions have been reported using [Cr(phen) 3 ] 3+ derivatives . Energy transfer to chromium(III) complexes has been investigated using luminescent [Cr(CN) 6 ] 3− , [Cr(ox) 3 ] 3− or trans ‐[Cr(CN) 2 (cyclam)] + acceptors in supramolecular architectures and in solid state materials (cyclam=1,4,8,11‐tetraazacyclotetradecane) . Vice versa, the luminescence of [Cr(alkynyl) 2 (cyclam)] + complexes is quenched by Dexter energy transfer to ferrocene.…”

Section: Introductionmentioning

confidence: 99%

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

et al. 2019

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Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, leading to reversible reductive chemistry. The excited state redox potential and lifetime of [Cr(tpe)2]3+ surpass those of the classical photosensitizer [Ru(bpy)3]2+ (bpy=2,2′‐bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n‐butyl)amine).

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Directional Energy Transfer in Nanocrystals of [Ru(2,2′‐bipyridine)₃][NaCr(oxalate)₃]

Abstract: Size-controlled nanocrystals (140 and 670 nm) and microcrystals (2.5 μm) of the three-dimensional oxalate network [Ru(bpy)

Cited by 7 publications

References 63 publications

Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

Synthesis and Characterisation of Luminescent [Cr^III₂L(μ‐carboxylato)]³⁺ Complexes with High‐Spin S=3 Ground States (L=N₆S₂ donor ligand)

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

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Directional Energy Transfer in Nanocrystals of [Ru(2,2′‐bipyridine)3]­[NaCr(oxalate)3]

Abstract: Size-controlled nanocrystals (140 and 670 nm) and microcrystals (2.5 μm) of the three-dimensional oxalate network [Ru(bpy)

Cited by 7 publications

References 63 publications

Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

Matrix Effects on Photoluminescence and Oxygen Sensitivity of a Molecular Ruby

Synthesis and Characterisation of Luminescent [CrIII2L(μ‐carboxylato)]3+ Complexes with High‐Spin S=3 Ground States (L=N6S2 donor ligand)

Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex

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Directional Energy Transfer in Nanocrystals of [Ru(2,2′‐bipyridine)₃][NaCr(oxalate)₃]

Synthesis and Characterisation of Luminescent [Cr^III₂L(μ‐carboxylato)]³⁺ Complexes with High‐Spin S=3 Ground States (L=N₆S₂ donor ligand)