Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(<scp>iii</scp>) complex I: synthesis, spectroscopy and static quantum chemistry

Dorn, Matthias; Kalmbach, Jens; Boden, Pit; Kruse, Ayla; Dab, Chahinez; Reber, Christian; Niedner‐Schatteburg, Gereon; Lochbrunner, Stefan; Gerhards, Markus; Seitz, Michael; Heinze, Katja

doi:10.1039/d1sc02137k

Cited by 34 publications

(26 citation statements)

References 103 publications

(145 reference statements)

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“…NIR-II spin-flip emission was also detected for the heteroleptic complex mer-V III Cl 3 (ddpd) V3 (Scheme 2, Table 2) in the solid state at room temperature with bands at 1102, 1219 and 1256 nm and a phosphorescence lifetime of 0.5 µs [144]. Ligand deuteration significantly increased the phosphorescence lifetime to 3.4 µs.…”

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 93%

“…ISC was found to occur within < 4.2 ps followed by VR with a time constant of 26 ps [128]. The rather slow ISC compared to V3 [144] or Cr III (acac) 3 Cr3 (Scheme 1) [68,146] was attributed to restrictions of vibrational modes along the ISC reaction coordinate imposed by the rigid substituted tren ligand [128].…”

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 95%

“…Interestingly, under hydrostatic pressure V3 showed a hypsochromic shift by + 10 cm -1 kbar -1 Scheme 2 Structures of luminescent V III and Cr IV complexes [62,128,130,131,142,144] in contrast to the bathochromic shifts found for Cr4 3+ . This positive shift was rationalized by the combined effect of changes in singlet energy and ground state splitting under pressure [144].…”

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 98%

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Spin-flip luminescence

Kitzmann

Moll

Heinze

2022

Photochem Photobiol Sci

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149

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In molecular photochemistry, charge-transfer emission is well understood and widely exploited. In contrast, luminescent metal-centered transitions only came into focus in recent years. This gave rise to strongly phosphorescent CrIII complexes with a d3 electronic configuration featuring luminescent metal-centered excited states which are characterized by the flip of a single spin. These so-called spin-flip emitters possess unique properties and require different design strategies than traditional charge-transfer phosphors. In this review, we give a brief introduction to ligand field theory as a framework to understand this phenomenon and outline prerequisites for efficient spin-flip emission including ligand field strength, symmetry, intersystem crossing and common deactivation pathways using CrIII complexes as instructive examples. The recent progress and associated challenges of tuning the energies of emissive excited states and of emerging applications of the unique photophysical properties of spin-flip emitters are discussed. Finally, we summarize the current state-of-the-art and challenges of spin-flip emitters beyond CrIII with d2, d3, d4 and d8 electronic configuration, where we mainly cover pseudooctahedral molecular complexes of V, Mo, W, Mn, Re and Ni, and highlight possible future research opportunities. Graphical abstract

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Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 93%

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 95%

Section: Spin-flip Emitters Based On Other Transition Metals and Elec...mentioning

confidence: 98%

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Spin-flip luminescence

Kitzmann

Moll

Heinze

2022

Photochem Photobiol Sci

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149

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“…The complex [VCl 3 (dppd)] likewise emits from the 1 E g / 1 T 2g manifold but seemingly only in the solid state. 33 Unlike in the homoleptic [V(ddpd) 2 ] 3+ congener, excited-state relaxation is strongly susceptible to ligand deuteration, confirming that multiphonon relaxation involving C−H oscillators is a major decay pathway. The large splitting of the electronic ground state, manifesting in the appearance of multiple 1 E g / 1 T 2g → 3 T 1g emission band maxima, likely further facilitates nonradiative excited-state relaxation by reducing the relevant energy gap.…”

Section: Llct Emitters: 3d 10 (Cu I ) Complexesmentioning

confidence: 93%

“…As the most abundant transition metal element in Earth’s crust, iron continuously attracts much attention, but two recent landmark studies , lead to unexpected insight that could revolutionize the field . Manganese and vanadium represent two comparatively abundant d-metal elements that only just appeared on the landscape of molecular complexes showing luminescence in solution at room temperature. − …”

Section: Introductionmentioning

confidence: 99%

Luminescent First-Row Transition Metal Complexes

Wegeberg

Wenger

2021

JACS Au

199

234

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Precious and rare elements have traditionally dominated inorganic photophysics and photochemistry, but now we are witnessing a paradigm shift toward cheaper and more abundant metals. Even though emissive complexes based on selected first-row transition metals have long been known, recent conceptual breakthroughs revealed that a much broader range of elements in different oxidation states are useable for this purpose. Coordination compounds of V, Cr, Mn, Fe, Co, Ni, and Cu now show electronically excited states with unexpected reactivity and photoluminescence behavior. Aside from providing a compact survey of the recent conceptual key advances in this dynamic field, our Perspective identifies the main design strategies that enabled the discovery of fundamentally new types of 3d-metal-based luminophores and photosensitizers operating in solution at room temperature.

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Charge‐Transfer und Spin‐Flip‐Zustände als sich ergänzende Gegensätze

Kitzmann

Heinze

2023

Angewandte Chemie

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Übergangsmetallkomplexe mit photoaktiven Charge‐Transfer‐Zuständen sind in der Literatur allgegenwärtig. Insbesondere [Ru(bpy)3]2+ (bpy=2,2′‐Bipyridin) mit seiner Metall‐zu‐Ligand‐Charge‐Transfer‐Emission hat sich als Schlüsselkomplex etabliert. Indes ist auch das Interesse an metallzentrierten Spin‐Flip‐Zuständen gestiegen, nachdem der molekulare Rubin [Cr(ddpd)2]3+ (ddpd=N,N′‐Dimethyl‐N,N′‐dipyridin‐2‐yl‐pyridin‐2,6‐diamin) Designprinzipien für intensive Emission von photostabilen Chrom(III)‐Komplexen enthüllt hat. In diesem Aufsatz werden die Eigenschaften von emissiven Charge‐Transfer‐ und Spin‐Flip‐Zuständen anhand der Prototypen [Ru(bpy)3]2+ bzw. [Cr(ddpd)2]3+ verglichen. Wir erörtern die angeregten Zustände, die Anpassbarkeit ihrer Energie und Lebensdauer sowie ihre Reaktion auf externe Stimuli. Schließlich werden die Stärken und Schwächen von Charge‐Transfer‐ und Spin‐Flip‐Zuständen in Anwendungen wie Photokatalyse und zirkular polarisierter Lumineszenz aufgezeigt.

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Ultrafast and long-time excited state kinetics of an NIR-emissive vanadium(iii) complex I: synthesis, spectroscopy and static quantum chemistry

Abstract: In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes...

Cited by 34 publications

References 103 publications

Spin-flip luminescence

Spin-flip luminescence

Luminescent First-Row Transition Metal Complexes

Charge‐Transfer und Spin‐Flip‐Zustände als sich ergänzende Gegensätze

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