Dinuclear Cu(I) Complex with Combined Bright TADF and Phosphorescence. Zero-Field Splitting and Spin–Lattice Relaxation Effects of the Triplet State

2018 ◽  
Vol 9 (11) ◽  
pp. 2848-2856 ◽  
Author(s):  
Alexander Schinabeck ◽  
Markus J. Leitl ◽  
Hartmut Yersin
Keyword(s):  
Triplet State ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Zero Field ◽  
Zero Field Splitting ◽  
Field Splitting ◽  
Spin Lattice ◽  
Relaxation Effects

Photophysics of the lowest triplet state in 2-benzoylpyridine crystals. II. Optically detected e. p. r. in zero and high magnetic fields

1979 ◽  
Vol 369 (1737) ◽  
pp. 187-206 ◽  
Keyword(s):  
Triplet State ◽  
Rate Constants ◽  
Radiative Decay ◽  
Dynamic Properties ◽  
Deep Trap ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Zero Field ◽  
Spin Lattice ◽  
Optically Detected

Optically detected zero-field resonance has been used to characterize the intrinsic and deep trap 3 nπ * states in single crystals of 2-benzoylpyridine at 4.2 K. The dynamic properties of these states were studied by means of time-resolved modulated phosphorescence (t. r. m. p.) and estimates for the rate constants for depopulation and spin-lattice relaxation of the magnetic sub-levels obtained by computer simulation. For all species, depopulation from ז z dominates, having rates of order 100 s -1 , but the ז x and ז y sub-states have substantial radiative activity. The orientations of the fine-structure tensors of the magnetic species were determined from high-field e. p. r. spectra. Assuming that z is parallel to C = O, excitation causes the C = O direction to change by 8 ± 2° for the intrinsic species and by an in-significant amount for the deep trap. These spectra also demonstrated that the intrinsic triplet state is mobile. This species is believed to be a polaron with slow intersite hopping rate. A maximum energy transfer rate of 10 4 -10 5 s -1 was found for transfer between translationally inequivalent sites symmetry-related by twofold rotation about the crystal b -axis. Rate estimates for transfer to the other two translationally inequivalent sites established the two dimensional nature of the polaron. The sign and shape of the zero-field resonances for the intrinsic species were found to depend on whether excitation was through S 1 or T 1 . From the parameters required to simulate the corresponding t. r. m. p. signals it is inferred that the changes are largely due to differences in the rate constants for non-radiative decay. The deep trap was shown to have an orientation and magnetic properties similar to those of the intrinsic species, and is believed to be a physical defect. It has radiative activity from the ז x sub-level which is significantly less than for the intrinsic species. Spin-lattice relaxation is fast for the mobile intrinsic species ( ca . 10 4 s -1 ) compared with the deep trap rate ( ca . 50 4 s -1 ). For the intrinsic species a field dependence for spin-lattice relaxation is apparent.

scholarly journals P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3415
Author(s):  
Thomas Hofbeck ◽  
Thomas A. Niehaus ◽  
Michel Fleck ◽  
Uwe Monkowius ◽  
Hartmut Yersin
Keyword(s):  
Quantum Yield ◽  
Decay Time ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Photo Luminescence ◽  
Delayed Fluorescence ◽  
Spin Lattice Relaxation ◽  
Zero Field ◽  
Triplet States ◽  
Spin Lattice

We present an overview over eight brightly luminescent Cu(I) dimers of the type Cu2X2(P∩N)3 with X = Cl, Br, I and P∩N = 2-diphenylphosphino-pyridine (Ph2Ppy), 2-diphenylphosphino-pyrimidine (Ph2Ppym), 1-diphenylphosphino-isoquinoline (Ph2Piqn) including three new crystal structures (Cu2Br2(Ph2Ppy)3 1-Br, Cu2I2(Ph2Ppym)3 2-I and Cu2I2(Ph2Piqn)3 3-I). However, we mainly focus on their photo-luminescence properties. All compounds exhibit combined thermally activated delayed fluorescence (TADF) and phosphorescence at ambient temperature. Emission color, decay time and quantum yield vary over large ranges. For deeper characterization, we select Cu2I2(Ph2Ppy)3, 1-I, showing a quantum yield of 81%. DFT and SOC-TDDFT calculations provide insight into the electronic structures of the singlet S1 and triplet T1 states. Both stem from metal+iodide-to-ligand charge transfer transitions. Evaluation of the emission decay dynamics, measured from 1.2 ≤ T ≤ 300 K, gives ∆E(S1-T1) = 380 cm−1 (47 meV), a transition rate of k(S1→S0) = 2.25 × 106 s−1 (445 ns), T1 zero-field splittings, transition rates from the triplet substates and spin-lattice relaxation times. We also discuss the interplay of S1-TADF and T1-phosphorescence. The combined emission paths shorten the overall decay time. For OLED applications, utilization of both singlet and triplet harvesting can be highly favorable for improvement of the device performance.

Spin-Gitter-Relaxation im Triplett-Zustand von Chinoxalin in Perdeutero-Naphthalin und zwei ähnlichen Mischkristallen

1975 ◽  
Vol 30 (6-7) ◽  
pp. 754-770 ◽  
Author(s):  
U. Konzelmann ◽  
D. Kilpper ◽  
M. Schwoerer
Keyword(s):  
Triplet State ◽  
Deep Trap ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Mixed Crystals ◽  
Spin Lattice Relaxation ◽  
Relaxation Processes ◽  
Shallow Trap ◽  
Field Range ◽  
Spin Lattice

Abstract Spin Lattice Relaxation in the Triplet State of Qainoxaline in Perdeuteronaphthalene and of two Similar Mixed Crystals The spin lattice relaxation in the excited triplet state of three mixed crystals was investigated: Quinoxaline in perdeutero-naphthalene, quinoxaline in naphthalene (X-traps) and quinoxaline in durene. They differ by the depth of their traps, which are shallow (90 cm -1), very shallow (60 cm -1) and deep (6600 cm -1), respectively. In order to identify the relaxation processes and the relaxation mechanism, the experiments were performed in the large magnetic field range be-tween 0.2 T and 5.4 T. By use of a non-resonant optical method and by ESR and ODMR it could be shown that at high fields the direct process (emission of resonant phonons) is the only efficient process up to 4.2 K. At low fields Raman-processes are dominant. Thereby the spin lattice relaxation probability per unit time, w, increases with the ninth power of the temperature in the shallow trap systems and with the fifth power in the deep trap system. By the analysis of the very strong anisotropy of w it could be shown that the efficient relaxation mechanism in the shallow trap systems is a guest-host-interaction modulated by phonons.

Time Domain Zero Field NMR and NQR

1986 ◽  
Vol 41 (1-2) ◽  
pp. 440-444 ◽  
Author(s):  
A. Bielecki ◽  
D. B. Zax ◽  
A. M. Thayer ◽  
J. M. Millar ◽  
A. Pines
Keyword(s):  
Time Domain ◽  
Relaxation Times ◽  
Low Frequency ◽  
High Sensitivity ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Zero Field ◽  
Spin Lattice ◽  
Field Cycling ◽  
The Time Domain

Field cycling methods are described for the time domain measurement of nuclear quadrupolar and dipolar spectra in zero applied field. Since these techniques do not involve irradiation in zero field, they offer significant advantages in terms of resolution, sensitivity at low frequency, and the accessible range of spin lattice relaxation times. Sample data are shown which illustrate the high sensitivity and resolution attainable. Comparison is made to other field cycling methods, and an outline of basic instrumental requirements is given.

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