A Near‐Infrared‐II Emissive Chromium(III) Complex

Sinha, Narayan; Jiménez, Juan‐Ramón; Pfund, Björn; Prescimone, Alessandro; Piguet, Claude; Wenger, Oliver S.

doi:10.1002/ange.202106398

Cited by 21 publications

(36 citation statements)

References 74 publications

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“…In fact, traditional noble metal complexes based on Ru(II), − Ir(III), − or Re(I) , have attracted much attention during the last decades and are still under constant development. However, the interest in complexes using more earth-abundant 3d metals such as Cr, − Fe, − Zn, , and Cu ,− is strongly increasing due to advantages in costs and availability.…”

Section: Introductionmentioning

confidence: 99%

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

et al. 2022

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In this study, we present a slight but surprisingly successful structural modification of the previously reported heteroleptic Cu(I) photosensitizer Cubiipo ([(xantphos)Cu(biipo)]PF6; biipo = 16H-benzo-[4′,5′]-isoquinolino-[2′,1′:1,2]-imidazo-[4,5-f]-[1,10]-phenanthrolin-16-one). As a key feature, biipo bears a naphthalimide unit at the back, which is directly fused to a phenanthroline moiety to extend the conjugated π-system. This ligand was now altered to include two additional methyl groups at the 2,9-positions at the phenanthroline scaffold. Comparing the novel Cudmbiipo complex to its predecessor, ultrafast transient absorption spectroscopy reveals the efficient suppression of a major deactivation pathway by stabilization of a transient triplet state. Furthermore, quantitative measurements of singlet oxygen evolution in solution confirmed that a larger fraction of the excited-state population is transferred to the photocatalytically active ligand-centered triplet 3LC state with a much longer lifetime of ∼30 μs compared to Cubiipo (2.6 μs). In addition, Cudmbiipo was compared with the well-established reference complex Cubcp ([(xantphos)Cu(bathocuproine)]PF6) in terms of its photophysical and photocatalytic properties by applying time-resolved femto- and nanosecond absorption, step-scan Fourier transform infrared (FTIR), and emission spectroscopies. Superior light-harvesting properties and a greatly enhanced excited-state lifetime with respect to Cubcp enable Cudmbiipo to be more active in exemplary photocatalytic applications, i.e., in the formation of singlet oxygen and the isomerization of (E)-stilbene.

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Section: Introductionmentioning

confidence: 99%

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

et al. 2022

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“…1067 nm) using ligand fields that combine optimised octahedral geometries with both σ- and π-donor/π-acceptor characteristics that potentially increase metal–ligand covalency. 13 This was achieved using a 3,6-di- tert -butyl-1,8-di(-pyridine-2-yl)-carbazole (dpc) ligand (Scheme 1) which imparts trans N–Cr–N bond angles of around 174° for [Cr(dpc) 2 ] + . Excitation at 450 nm yielded an emission peaking at 1067 nm (with dual lifetimes of 1.4 and 6.3 μs) assigned to a possible admixture of 2 LMCT/ 2 E excited states.…”

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confidence: 99%

“…+0.46 V vs. Fc 0/+ which was ascribed to a Cr 3+/4+ redox couple. 13 Polypyridyl Cr( iii ) complexes such as [Cr(bipy) 2 ] 3+ (ref. 25) and [Cr(terpy) 2 ] 3+ (ref.…”

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confidence: 99%

“…Previous work on related [Cr(dpc) 2 ] + has proposed, through computational studies, that a 2 LMCT band may also contribute in this region. 13…”

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confidence: 99%

“…Previous work on related [Cr(dpc) 2 ] + has proposed, through computational studies, that a 2 LMCT band may also contribute in this region. 13 For the luminescence studies, the complexes were prepared in MeCN and excited using 430 nm irradiation. As shown in Fig.…”

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confidence: 99%

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Long-lived, near-IR emission from Cr(iii) under ambient conditions

et al. 2022

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Photoluminescent Cu(I) Assemblies with High‐Temperature Solid‐State Transitions as a New Class of Thermic History Tracers

Schlachter,

Moutier,

Utrera‐Melero

et al. 2024

Advanced Optical Materials

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The preparation of a new series of luminescent one dimensional coordination polymers based on the association of a photoactive tetrametallic metallacycle Cu(I) precursor with pyridyl‐caped ditopic linkers is reported. In spite of related molecular architectures, these coordination polymers present upon Ultraviolet visible light photoexcitation markedly contrasted solid‐state luminescence behaviors including eye‐perceived colors of the emitted light spanning all over the visible spectrum. Solid‐state temperature‐dependent photophysical measurements and Time‐dependent density‐functional theory calculations have been conducted to identify the relaxation pathways lying in these assemblies. Very importantly, thermal stability studies at high temperature for all these derivatives reveal an irreversible post‐synthetic solid‐state transition that impacts dramatically the photophysical properties of these newly obtained phases, highlighting an innovative family of stimuli‐sensitive materials that can witness the exceeding of critical temperatures in their environment.

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A Near‐Infrared‐II Emissive Chromium(III) Complex

Cited by 21 publications

References 74 publications

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

Long-lived, near-IR emission from Cr(iii) under ambient conditions

Photoluminescent Cu(I) Assemblies with High‐Temperature Solid‐State Transitions as a New Class of Thermic History Tracers

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