Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand

Kögel, Julius F.; Kusaka, Shinpei; Sakamoto, Ryota; Iwashima, Toshiki; Tsuchiya, Mizuho; Toyoda, Ryojun; Matsuoka, Ryota; Tsukamoto, Takamasa; Yuasa, Junpei; Kitagawa, Yasutaka; Kawai, Tsuyoshi; Nishihara, Hiroshi

doi:10.1002/ange.201509411

Cited by 29 publications

(9 citation statements)

References 49 publications

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“…These selection rules are very favorable for SF emitters, and result in g lum values up to 0.20, [64, 65, 239, 265, 266] whereas CT emitters typically have values below 0.005 [238, 260, 267, 268] . The Δ and Λ enantiomers of [Ru(bpy) 3 ] 2+ show only weak CPL, with | g lum |=0.0007 at 625 nm (Figure 8).…”

Section: Applicationsmentioning

confidence: 99%

Charge‐Transfer and Spin‐Flip States: Thriving as Complements

Kitzmann

Heinze

2023

Angew Chem Int Ed

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Transition metal complexes with photoactive charge-transfer excited states are pervasive throughout the literature. In particular, [Ru(bpy) 3 ] 2 + (bpy = 2,2'-bipyridine), with its metal-to-ligand charge-transfer emission, has been established as a key complex. Meanwhile, interest in so-called spin-flip metal-centered states has risen dramatically after the molecular ruby [Cr(ddpd) 2 ] 3 + (ddpd = N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridine-2,6-diamine) led to design principles to access strong, long-lived emission from photostable chromium(III) complexes. This Review contrasts the properties of emissive charge-transfer and spin-flip states by using [Ru(bpy) 3 ] 2 + and [Cr(ddpd) 2 ] 3 + as prototypical examples. We discuss the relevant excited states, the tunability of their energy and lifetimes, and their response to external stimuli. Finally, we identify strengths and weaknesses of charge-transfer and spin-flip states in applications such as photocatalysis and circularly polarized luminescence.

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Section: Applicationsmentioning

confidence: 99%

Charge‐Transfer and Spin‐Flip States: Thriving as Complements

Kitzmann

Heinze

2023

Angew Chem Int Ed

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“…While Cu I is beneficially redox‐active, the high oxidation potential of Zn II forbids the formation of MLCT states. In addition, the majority of photoactive zinc(II) complexes is homoleptically coordinated, and thus fluorescent from ligand‐centred ( 1 LC) states [30–32] …”

Section: Introductionmentioning

confidence: 99%

An Air‐ and Moisture‐stable Zinc(II) Carbene Dithiolate Dimer Showing Fast Thermally Activated Delayed Fluorescence and Dexter Energy Transfer Catalysis**

Mrózek

Mitra

Hupp

et al. 2023

Chemistry A European J

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“…The most frequently observed emission type in Zn II complexes until now is ligand-based fluorescence, for example, in many dipyrrin-based compounds, − complexes with benzothiazole ligands, − as well as with other nitrogen and oxygen donor ligands, , or phosphines . Possible applications of fluorescent Zn II compounds in electroluminescence, ,− including organic light-emitting diodes (OLEDs), − circularly polarized luminescence, sensing, or cell imaging, have attracted interest . Similarly, aggregation-induced emission − as well as thermally activated delayed fluorescence (TADF) received substantial attention with Zn II complexes. − …”

Section: Introductionmentioning

confidence: 99%

Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion

Kübler

Pfund

Wenger

2022

JACS Au

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Many CuI complexes have luminescent triplet charge-transfer excited states with diverse applications in photophysics and photochemistry, but for isoelectronic ZnII compounds, this behavior is much less common, and they typically only show ligand-based fluorescence from singlet π–π* states. We report two closely related tetrahedral ZnII compounds, in which intersystem crossing occurs with appreciable quantum yields and leads to the population of triplet excited states with intraligand charge-transfer (ILCT) character. In addition to showing fluorescence from their initially excited 1ILCT states, these new compounds therefore undergo triplet–triplet energy transfer (TTET) from their 3ILCT states and consequently can act as sensitizers for photo-isomerization reactions and triplet–triplet annihilation upconversion from the blue to the ultraviolet spectral range. The photoactive 3ILCT state furthermore facilitates photoinduced electron transfer. Collectively, our findings demonstrate that mononuclear ZnII compounds with photophysical and photochemical properties reminiscent of well-known CuI complexes are accessible with suitable ligands and that they are potentially amenable to many different applications. Our insights seem relevant in the greater context of obtaining photoactive compounds based on abundant transition metals, complementing well-known precious-metal-based luminophores and photosensitizers.

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Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand

Cited by 29 publications

References 49 publications

Charge‐Transfer and Spin‐Flip States: Thriving as Complements

Charge‐Transfer and Spin‐Flip States: Thriving as Complements

An Air‐ and Moisture‐stable Zinc(II) Carbene Dithiolate Dimer Showing Fast Thermally Activated Delayed Fluorescence and Dexter Energy Transfer Catalysis**

Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion

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