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Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

ABSTRACT: OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu-C and Cu-P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05?Å increase of the shortest Cu-Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores.

SUBMITTER: Smolentsev G

PROVIDER: S-EPMC7195477 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

Smolentsev Grigory G Milne Christopher J CJ Guda Alexander A Haldrup Kristoffer K Szlachetko Jakub J Azzaroli Nicolo N Cirelli Claudio C Knopp Gregor G Bohinc Rok R Menzi Samuel S Pamfilidis Georgios G Gashi Dardan D Beck Martin M Mozzanica Aldo A James Daniel D Bacellar Camila C Mancini Giulia F GF Tereshchenko Andrei A Shapovalov Victor V Kwiatek Wojciech M WM Czapla-Masztafiak Joanna J Cannizzo Andrea A Gazzetto Michela M Sander Mathias M Levantino Matteo M Kabanova Victoria V Rychagova Elena E Ketkov Sergey S Olaru Marian M Beckmann Jens J Vogt Matthias M

Nature communications 20200501 1

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu-C and Cu-P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, ...[more]

PMID: 32358505

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Project description:The structure of 30 monosubstituted benzenes in the first excited triplet T1 state was optimized with both unrestricted (U) and restricted open shell (RO) approximations combined with the ?B97XD/aug-cc-pVTZ basis method. The substituents exhibited diverse ?- and ?-electron-donating and/or -withdrawing groups. Two different positions of the substituents are observed in the studied compounds in the T1 state: one distorted from the plane and the other coplanar with a quinoidal ring. The majority of the substituents are ?-electron donating in the first group while ?-electron withdrawing in the second one. Basically, U- and RO-?B97XD approximations yield concordant results except for the B-substituents and a few of the planar groups. In the T1 state, the studied molecules are not aromatic, yet aromaticity estimated using the HOMA (harmonic oscillator model of aromaticity) index increases from ca. -0.2 to ca. 0.4 with substituent distortion, while in the S1 state, they are only slightly less aromatic than in the ground state (HOMA ?0.8 vs ?1.0, respectively). Unexpectedly, the sEDA(T1) and pEDA(T1) substituent effect descriptors do not correlate with analogous parameters for the ground and first excited singlet states. This is because in the T1 state, the geometry of the ring changes dramatically and the sEDA(T1) and pEDA(T1) descriptors do not characterize only the functional group but the entire molecule. Thus, they cannot provide useful scales for the substituents in the T1 states. We found that the spin density in the T1 states is accumulated at the Cipso and Cp atoms, and with the substituent deformation angle, it nonlinearly increases at the former while decreases at the latter. It appeared that the gap between singly unoccupied molecular orbital and singly occupied molecular orbital (SUMO-SOMO) is determined by the change of the SOMO energy because the former is essentially constant. For the nonplanar structures, SOMO correlates with the torsion angle of the substituent and the ground-state pEDA(S0) descriptor of the ?-electron-donating substituents ranging from 0.02 to 0.2 e. Finally, shapes of the SOMO-1 instead of SOMO frontier orbitals in the T1 state somehow resemble the highest occupied molecular orbital ones of the S0 and S1 states. For several planar systems, the shape of the U- and RO-density functional theory-calculated SOMO-1 orbitals differs substantially.

Dataset Information

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

Publications

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

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