Intense Red‐Blue Luminescence Based on Superfine Control of Metal–Metal Interactions for Self‐Assembled Platinum(II) Complexes

Saito, Daisuke; Ogawa, Tomohiro; Yoshida, Masaki; Takayama, Junichi; Hiura, Satoshi; Murayama, Akihiro; Kobayashi, Atsushi; Kato, Masako

doi:10.1002/ange.202008383

Cited by 6 publications

(2 citation statements)

References 59 publications

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“…3.477(2) Å). 31 This result is consistent with the RIXS measurements. The quantum yields of the region between 450 and 700 nm of 1 at RT and 77 K were estimated to be 0.8 and 18.3%, respectively.…”

Section: Resultssupporting

confidence: 90%

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

Yoshida

Shabana

Izuogu

et al. 2022

Preprint

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Theoretical calculations are typically utilized for examining intermetallic interactions. However, to validate theory, experimental confirmation of the existence of these interactions is necessary. We synthesized new heterometallic Ln–Pt complexes, NEt4{[Pt(PhSAc)4]Ln[(PhSAc)4Pt]}·2DMF (Ln: lanthanoid = Gd (1), Tb (2), Dy (3), PhSAc = benzothioacetate, NEt4 = tetraethylammonium), in which both diamagnetic Pt(II) ions interact with the central Ln(III) ion. Typically, these interactions are not detected, because the distance between Ln and Pt atoms (~3.6 Å) is much larger than the covalent radius (~3.3 Å) and ionic radius (~3.10 Å). Pt-LIII resonant inelastic X-ray scattering (RIXS) analysis was conducted to experimentally confirm the unique influence of the hidden Ln–Pt interaction on the luminescence of the Tb–Pt molecule, where the interaction induced emission properties in the Tb and Pt ions, with high quantum yield (59%). Quantum theory of atoms in molecules (QTAIM) analysis was also used to confirm the experimental results. RIXS analysis allowed the identification of several distinctive characteristics of the coordination environment, including the existence of heterometallic interactions, that affected the observed luminescence.

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Section: Resultssupporting

confidence: 90%

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

Yoshida

Shabana

Izuogu

et al. 2022

Preprint

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“…Complicated changes often occur in chromic complexes that respond to weak stimuli. Recently, in-depth investigations of multi-stimuli responses and multi-chromic phenomena were reported (Ni et al, Martı ´nez- Junquera et al, 2022;Shigeta et al, 2023;Morimoto et al, 2023).…”

Section: Pt(ii) Complexes Exhibiting Assembly-induced Luminescence 21...mentioning

confidence: 99%

Chromic soft crystals based on luminescent platinum(II) complexes

Kato

2024

IUCrJ

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Platinum(II) complexes of square-planar geometry are interesting from a crystal engineering viewpoint because they exhibit strong luminescence based on the self-assembly of molecular units. The luminescence color changes in response to gentle stimuli, such as vapor exposure or weak mechanical forces. Both the molecular and the crystal designs for soft crystals are critical to effectively generate the chromic luminescence phenomenon of Pt(II) complexes. In this topical review, strategies for fabricating chromic luminescent Pt(II) complexes are described from a crystal design perspective, focusing on the structural regulation of Pt(II) complexes that exhibit assembly-induced luminescence via metal–metal interactions and structural control of anionic Pt(II) complexes using cations. The research progress on the evolution of various chromic luminescence properties of Pt(II) complexes, including the studies conducted by our group, are presented here along with the latest research outcomes, and an overview of the frontiers and future potential of this research field is provided.

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Simple Phenazine‐Based Compounds Realizing Superior Multicolored Emission

Xie

Cai

Wang

et al. 2022

Advanced Optical Materials

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are commonly found in Cu [3][4][5][6] and noble metal (e.g., Ir, Pt) complexes. [7][8][9][10][11][12] Comparing with fluorescence materials, the predominant advantage of phosphorescence materials is their internal quantum efficiency that can approach 100%. [13][14][15] However, high cost is a barrier which cannot be circumvented for commercial manufacture. Besides above two categories of materials, pure organic molecules, for instance, thermally activated delayed fluorescence (TADF) materials, are regarded as promising candidates for organic lightemitting diodes (OLEDs). TADF can harness almost 100% exciton accessing to reverse intersystem crossing (RISC) path, thereby achieving relatively superior performance in devices. [16,17] Significant investigations have been performed to get the high-performance TADF materials in past decades. [14,16,[18][19][20][21][22][23][24][25] Generally, TADF materials should have a considerably small energy difference (ΔE ST < 0.5 eV) between the lowest singlet (S 1 ) and triplet (T 1 ) states. [16] This requires the lowest singlet excited state to have a small orbital overlap integral (S if = 〈Φ i |Φ f 〉) between initial (Φ i ) and final (Φ f ) state orbits, corresponding to the degree of spatial overlap of the orbits, thereby gaining a small exchange integral (2J if = ΔE ST ). [20] Based on this strategy, many researchers tended to modify the subject (acceptor) by integrating more electron donors (Ds), [26][27][28] aiming to utilize the steric hindrance of donors to separate the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs). Some previous works are preferred to use special donors, such as 1,8-dimethylcarbazole, [29][30][31] to make a large dihedral angle between donor and acceptor (A). Regardless of which method was used, to achieve high efficiency performance, most compounds either experienced arduously picking of specific subjects (acceptors) that were tedious to synthesize, [21] or were coupled with more and even different donors. [32,33] Meanwhile, even though the interest in TADF materials is shifting to the operational lifetime, [34] color purity, [23] reverse intersystem crossing rate, and so on, [31,[34][35][36] however, according to recent works reported by Ma [37] and Adachi and co-workers, [24,38] new mechanisms about hybrid local and charge-transfer (HLCT)-type TADF have been proposed. We hope that depending on this work, these new mechanisms could be applied to the conventional TADF configuration, further paving the way for the follow-up studies of the mechanisms of TADF.A new family of phenazine-based compounds is synthesized to achieve multicolored emission from deep blue (418 nm) to red (625 nm). Emitters have unique hybrid local and charge-transfer excited states for S 1 , T 1 , T 2 , and even higher-layer excited states, respectively, while all emitters possess thermally activated delayed fluorescence (TADF) nature. The rigid structure of phenazine and steric hindrance of donors are sufficiently utilized to supp...

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Intense Red‐Blue Luminescence Based on Superfine Control of Metal–Metal Interactions for Self‐Assembled Platinum(II) Complexes

Cited by 6 publications

References 59 publications

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

Hidden Heterometallic Interaction Emerges from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

Chromic soft crystals based on luminescent platinum(II) complexes

Simple Phenazine‐Based Compounds Realizing Superior Multicolored Emission

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