Deuterated Molecular Ruby with Record Luminescence Quantum Yield

Wang, Cui; Otto, Sven; Dorn, Matthias; Kreidt, Elisabeth; Lebon, Jakob; Sršan, Laura; Martino‐Fumo, Patrick Di; Gerhards, Markus; Resch‐Genger, Ute; Seitz, Michael; Heinze, Katja

doi:10.1002/anie.201711350

Cited by 103 publications

(188 citation statements)

References 73 publications

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“…This complex can be considered am olecular ruby analogue due to its exceptionally high quantum yields of 10-14 %i ns olution at room temperature and up to 30 %f or deuterated derivatives. [12,13] These molecular rubies have emerging applications in photocatalysis [14] and sensing. [15,16] Thet wo sharp spin-flip transitions 2 E!…”

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confidence: 99%

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Molecular Ruby under Pressure

et al. 2018

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The intensely luminescent chromium(III) complexes [Cr(ddpd) ] and [Cr(H tpda) ] show surprising pressure-induced red shifts of up to -15 cm kbar for their sharp spin-flip emission bands (ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine; H tpda=2,6-bis(2-pyridylamino)pyridine). These shifts surpass that of the established standard, ruby Al O :Cr , by a factor of 20. Beyond the common application in the crystalline state, the very high quantum yield of [Cr(ddpd) ] enables optical pressure sensing in aqueous and methanolic solution. These unique features of the molecular rubies [Cr(ddpd) ] and [Cr(H tpda) ] pave the way for highly sensitive optical pressure determination and unprecedented molecule-based pressure sensing with a single type of emitter.

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confidence: 99%

“…4 A 2 emission at 775 nm, which is strongly redshifted relative to the corresponding transition in Cr 3+ -doped solids. [12][13][14][15][16] Va riablepressure luminescence spectra of [Cr(ddpd) 2 ][BF 4 ] 3 are depicted in Figures 1, S1, and S2 (Supporting Information) for both the crystalline sample and as ample dissolved in water.…”

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Molecular Ruby under Pressure

et al. 2018

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“…These values are slightly lower than the emission quantumy ields and lifetimes of 1 3 + + ,d emonstrating the luminescence quenching of the NH oscillators in 2 3 + + through multiphonon relaxation. [7,14] This effect will be discussedi nm ore detail below. (2) 2.059 2.049(2) 2.022 N1-Cr1-N38 6.94 (9) 88.20 (10) 88.07 85.13(8) 87.87 N1-Cr1-N51 73.52 (9) 176.07 (10)1 76. 20 171.86(8) 175.83 N6-Cr1-N88 6.94 (9) 88.20 (10) 88.07 85.89(8) 88.63 N6-Cr1-N10 173.52 (9) 176.07 (10) (3) ---N4···O1 2.908 (3) 3.036 (4) ---N7···O1 2.908 (3) 3.036 (4) ---N9···O2 2.892 (3) 2.982 (3) --- In the presence of molecular oxygen, the luminescence quantum yields of 2 3 + + decrease by factorso f4 .2 and 11.0 in H 2 Oa nd CH 3 CN, respectively.D exter energy transfer to 3 O 2 occurs, giving 1 O 2 ,s imilart ot he excited-state reactivity of 1 3 + + .…”

Section: Opticalpropertiesmentioning

confidence: 98%

“…Clearly,t he CH oscillators of CH 3 CN are less efficient in the excited-state decay of 2 3 + + , [D 4 ]-2 3 + + ,a nd 1 3 + + . [14] As traightforward explanation is the rather large distance of approximately r = 6.5 of the CH 3 CN oscillators to the chromium center in the solid-state structure of [Cr(H 2 tpda) 2 ][ClO 4 ] 3 ·CH 3 CN.…”

Section: Acid-base Chemistrymentioning

confidence: 99%

“…Consequently,t heir deuteration yields the strongest luminescence enhancement. [14] First applications of the strongly luminescent "molecular ruby" comprise optical temperature sensing in solution,i nm icelles,o ri nn anoparticles with as ingle dye based on its two NIR emission bands, [15a] opticalp ressure sensing in the solid state and in solution, [15b] and selectivee nergy transfer to triplet oxygen, yielding singlet oxygen for organic photoinduced transformations. [16] Further applicationso f1 3 + + and its derivatives are envisioned for the nearfuture.…”

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confidence: 99%

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A Strongly Luminescent Chromium(III) Complex Acid

Otto

Förster

Wang

et al. 2018

Chemistry A European J

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The synthesis, structure, reactivity, and photophysical properties of a novel acidic, luminescent chromium(III) complex [Cr(H tpda) ] (2 ) bearing the tridentate H tpda (2,6-bis(2-pyridylamino)pyridine) ligand are presented. Excitation of 2 at 442 nm results in strong, long-lived NIR luminescence at 782 nm in water and in acetonitrile. X-ray diffraction analysis and IR spectroscopy reveal hydrogen-bonding interactions of the counter ions to the NH groups of 2 in the solid state. Deprotonation of the NH groups of 2 by using a non-nucleophilic Schwesinger base in CH CN switches off the luminescence. Re-protonation by using HClO restores the emission. In water, the pK value of 2 amounts to 8.8, yet deprotonation is not reversible in the presence of hydroxide ions. Dioxygen quenches the emission of 2 , but to a weaker extent than expected. This is possibly due to the strong ion-pairing properties of 2 even in solution, reducing the energy transfer efficiency to O . Deuteration of the NH groups of 2 approximately doubles the quantum yield and lifetime in water, demonstrating the importance of multiphoton relaxation in these NIR emitters.

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Near‐Infrared OLEDs Based on Functional Pyrazinyl Azolate Os(II) Phosphors and Deuteration

Peng

Yeh

Wang

et al. 2022

Advanced Optical Materials

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Their advantages included cost-effectiveness and improved capability in miniaturization and in making flexible devices. [2] In the future, it is expected that OLED will be pivotal for emerging applications such as sensing and imaging, [3] phototherapy, [4] and even security identification, [5] to which the nearinfrared (NIR) emissions are both invisible to human eyes and with an increased penetration depth into our tissue. Therefore, electroluminescence (EL) with peak wavelengths beyond 700 nm will be needed in the successful fabrication of this class of OLED. [6] Moreover, an emission peak max. (λ max ) of over 800 nm (1.6 eV) is essential for achieving an emission onset at 700 nm (1.8 eV) and to be fully invisible to human. However, when the emission gap is shifted toward the deep red and NIR regions, the vibrational relaxation can be facilitated through the overlap between the zero vibration level of the lowest-lying singlet (S 1 ) or triplet (T 1 ) state and the higher vibration levels of the ground (S 0 ) state. Therefore, NIR emitting materials typically suffer from inferior emission efficiency, according to the above mentioned energy gap law. [7] Generally speaking, fluorescent emitters, [8] thermally activated delayed fluorescent (TADF) molecules [9] and transitionmetal complexes [10] have been promising candidates for NIR emission. To name a few, the BF 2 curcuminoid derivatives were employed in fabrication of NIR TADF OLED, showing Near-infrared (NIR) emitting Os(II) complexes [Os(L1) 2 (PPhMe 2 ) 2 ] (tz1), [Os(L2) 2 (PPhMe 2 ) 2 ] (tz2), and [Os(L3) 2 (PPhMe 2 ) 2 ] (tz3), bearing dual (1H-1,2,4-triazol-5-yl)pyrazine chromophoric chelates, are successfully developed. These pyrazine chelates tzn (n = 1, 2, 3) differ by the location and number of 4-(trifluoromethyl)phenyl appendage(s) on pyrazine, and the associated Os(II) complexes exhibit bathochromic shifted emission, higher quantum yield, and increased radiative lifetime in comparison to parent complex [Os(fprtz) 2 (PMe 2 Ph) 2 ] (tz0). Moreover, partially deuterated pyrazine chelate L1-d is prepared using post-synthetic deuteration, from which the Os(II) complex tz1 shows a photoluminescence quantum yield (PLQY) of 12.2% in co-doped 4,4′-bis(N-carbazolyl)biphenyl (CBP) thin film at 3 wt%. Further, the partially deuterated tz1-d exhibits a notable increase in PLQY to 17.8% upon co-deposited into CBP thin film, confirming the influence of C-H(D) stretching vibrations on the non-radiative transition processes. Finally, tz1-d is demonstrated to be suitable in the fabrication of efficient NIR organic light-emitting diodes (OLEDs), from which max. external quantum efficiency of 3.77% and max. radiance of 24.1 W sr -1 m -2 are recorded for emission with peak maximum at 776 nm. These experiments confirm the suppression of C-H vibration caused quenching by deuteration, which should be broadly applicable to the OLED emitters, especially in the NIR region.

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Deuterated Molecular Ruby with Record Luminescence Quantum Yield

Cited by 103 publications

References 73 publications

Molecular Ruby under Pressure

Molecular Ruby under Pressure

A Strongly Luminescent Chromium(III) Complex Acid

Near‐Infrared OLEDs Based on Functional Pyrazinyl Azolate Os(II) Phosphors and Deuteration

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