The central role of the metal ion for photoactivity: Zn– <i>vs.</i> Ni–Mabiq

Lauenstein, Raphael; Mader, Sophie L.; Derondeau, Henrieta; Esezobor, Oaikhena Zekeri; Block, Matthias; Römer, Armin J.; Jandl, Christian; Riedle, Eberhard; Kaila, Ville R. I.; Hauer, Jürgen; Thyrhaug, Erling; Hess, Corinna R.

doi:10.1039/d0sc06096h

Cited by 15 publications

(21 citation statements)

References 54 publications

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“…32,46,47,159,160 In parallel, considerable progress has been made toward 3d 8 MLCT luminophores based on Ni II , though in this case the breakthrough has not yet been made in the sense that room-temperature MLCT emission has not been achievable until now. 49,109 A paradigm change occurred with the recent emergence of highly emissive two-coordinate Cu I complexes which are LLCT luminophores (Figure 7b), [37][38][39]42,45 and with the discovery of Mn IV and Fe III LMCT emitters (Figure 7a). 29,30,119 The reversal of the charge transfer direction when going from MLCT to LMCT has direct consequences for possible applications in dye-sensitized solar cells; 161 yet as far as the luminescence properties are concerned, LMCT or LLCT emitters seem highly competitive with MLCT luminophores.…”

Section: Discussionmentioning

confidence: 99%

“…Other new developments in Ni II photochemistry involve the use of macrocyclic ligands, but no emission has been reported so far. 108,109 4. LMCT EMITTERS: 3d 0 (Sc III ), 3d 3 (Mn IV ), 3d 5 (Fe III ), AND 3d 6 (Co III ) COMPLEXES Energetically low-lying LMCT states call for electron-rich ligands and electron-deficient metals.…”

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

confidence: 99%

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Luminescent First-Row Transition Metal Complexes

Wegeberg

Wenger

2021

JACS Au

180

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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Section: Discussionmentioning

confidence: 99%

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

confidence: 99%

Luminescent First-Row Transition Metal Complexes

Wegeberg

Wenger

2021

JACS Au

180

234

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“…One of us has previously developed the solution chemistry of a series of mono- and bimetallic Mabiq complexes. Monometallic M-Mabiq complexes (e.g., M = Fe, Co, Ni, Cu, and Zn) with formal oxidation states ranging from 0 to III were isolated. − Our studies demonstrated that both the mono- and bimetallic compounds are photoactive. , Notably, the Co-Mabiq complex acts as an electrocatalyst for H 2 evolution, while Ni-Mabiq enables photocatalytic C–C bond formation. , …”

Section: Introductionmentioning

confidence: 78%

“…37−41 Our studies demonstrated that both the mono-and bimetallic compounds are photoactive. 41,42 Notably, the Co-Mabiq complex acts as an electrocatalyst for H 2 evolution, 43 while Ni-Mabiq enables photocatalytic C−C bond formation. 40,42 The tethering of Mabiq molecules on well-defined solid supports has not yet been explored.…”

Section: ■ Introductionmentioning

confidence: 99%

“…41,42 Notably, the Co-Mabiq complex acts as an electrocatalyst for H 2 evolution, 43 while Ni-Mabiq enables photocatalytic C−C bond formation. 40,42 The tethering of Mabiq molecules on well-defined solid supports has not yet been explored. The low-or unsymmetric Mabiq platform (Figure 1) with its two metal coordination sites bears promise for a richer two-dimensional (2-D) coordination chemistry 44 than the abovementioned tetrapyrrole complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

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The Flexible On-Surface Self-Assembly of a Low-Symmetry Mabiq Ligand: An Unconventional Metal-Assisted Phase Transformation on Ag(111)

et al. 2021

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The self-assembly of metal−organic complexes and networks of increasing complexity on solid surfaces is important for their application in a variety of fields, such as catalysis, sensing, and molecular magnetism. Here, we have selected a low-symmetry, freebase macrocyclic biquinazoline ligand, H-Mabiq, which upon metalation has the potential to incorporate cations in two different coordination sites, affording multi-valency and multielectron transfer capacity. We show that H-Mabiq molecules readily self-assemble onto the Ag(111) surface at room temperature, forming a well-ordered monolayer of closely packed molecules. Upon increasing the temperature, a new phase with a different long-range order and molecular packing is obtained. By means of scanning tunneling microscopy and photoelectron spectroscopy, we show that this new phase is characterized by a distinctive silver-bridged dimeric motif, entailing a Ag adatom accommodated at the peripheral coordination site of two opposing H-Mabiq molecules. Thus, the present work reveals the ability of the bio-inspired Mabiq ligands to form surface-confined two-dimensional assemblies incorporating metal adatoms. The results bode promise for the use of metalcontaining Mabiq compounds to engineer regular bimetallic arrays with atomic precision.

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

et al. 2021

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The combination of p-donating amido with paccepting pyridine coordination units in at ridentate chelate ligand causes astrong nephelauxetic effect in ahomoleptic Cr III complex, which shifts its luminescence to the NIR-II spectral range.P reviously explored Cr III polypyridine complexes typically emit between 727 and 778 nm (in the red to NIR-I spectral region), and ligand design strategies have so far concentrated on optimizing the ligand field strength. The present work takes af undamentally different approach and focusses on increasing metal-ligand bond covalence to shift the ruby-like 2 Ee mission of Cr III to 1067 nm at 77 K.

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The central role of the metal ion for photoactivity: Zn– vs. Ni–Mabiq

Abstract: Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts...

Cited by 15 publications

References 54 publications

Luminescent First-Row Transition Metal Complexes

Luminescent First-Row Transition Metal Complexes

The Flexible On-Surface Self-Assembly of a Low-Symmetry Mabiq Ligand: An Unconventional Metal-Assisted Phase Transformation on Ag(111)

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

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