<i>meta</i>-Terphenyl linked donor–π–acceptor dyads: intramolecular charge transfer controlled by electron acceptor group tuning

Kim, Minji; Ahn, Mina; Chae, Minjung; Kim, Sang-Hyun; Kim, Daehoon; Wee, Kyung‐Ryang

doi:10.1039/d1ra06602a

Cited by 6 publications

(4 citation statements)

References 77 publications

(89 reference statements)

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“…Regarding PY2 and PY3, LUMOs are localized partly on the pyrazolo[1,5-a]pyrimidine acceptor moiety and largely on the phenyl π-spacer. In contrast, the PY1 LUMO is localized only in the acceptor core, suggesting a stronger acceptor character of pyrazolo[1,5-a]pyrimidine with a substitution in position 3 compared to the other substitutions [69]. In addition, the theoretical calculated HOMO/LUMO values of As illustrated in Figure 4, the frontier molecular orbitals indicate that the PY1, PY2 and PY3 HOMOs are primarily localized on the 3,6-CzDMPA donor group.…”

Section: Dft Calculationsmentioning

confidence: 95%

“…Regarding PY2 and PY3, LUMOs are localized partly on the pyrazolo[1,5-a]pyrimidine acceptor moiety and largely on the phenyl π-spacer. In con-trast, the PY1 LUMO is localized only in the acceptor core, suggesting a stronger acceptor character of pyrazolo[1,5-a]pyrimidine with a substitution in position 3 compared to the other substitutions [69]. In addition, the theoretical calculated HOMO/LUMO values of PY1, PY2 and PY3 are −4.19/−2.02, −4.30/−1.93 and −4.35/−1.92, respectively, and the energy gap consequently increases in the order of PY1 (2.17 eV) < PY2 (2.37 eV) < PY3 (2.43 eV), following the same trend as the UV-visible characterizations (E gap opt = 2.25, 2.33 and 2.40 eV for PY1, PY2 and PY3, respectively).…”

Section: Dft Calculationsmentioning

confidence: 99%

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D-π-A-Type Pyrazolo[1,5-a]pyrimidine-Based Hole-Transporting Materials for Perovskite Solar Cells: Effect of the Functionalization Position

et al. 2022

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Donor–acceptor (D–A) small molecules are regarded as promising hole-transporting materials for perovskite solar cells (PSCs) due to their tunable optoelectronic properties. This paper reports the design, synthesis and characterization of three novel isomeric D-π-A small molecules PY1, PY2 and PY3. The chemical structures of the molecules consist of a pyrazolo[1,5-a]pyrimidine acceptor core functionalized with one 3,6-bis(4,4′-dimethoxydiphenylamino)carbazole (3,6-CzDMPA) donor moiety via a phenyl π-spacer at the 3, 5 and 7 positions, respectively. The isolated compounds possess suitable energy levels, sufficient thermal stability (Td > 400 °C), molecular glass behavior with Tg values in the range of 127–136 °C slightly higher than that of the reference material Spiro-OMeTAD (126 °C) and acceptable hydrophobicity. Undoped PY1 demonstrates the highest hole mobility (3 × 10−6 cm2 V−1 s−1) compared to PY2 and PY3 (1.3 × 10−6 cm2 V−1 s−1). The whole isomers were incorporated as doped HTMs in planar n-i-p PSCs based on double cation perovskite FA0.85Cs0.15Pb(I0.85Br0.15)3. The non-optimized device fabricated using PY1 exhibited a power conversion efficiency (PCE) of 12.41%, similar to that obtained using the reference, Spiro-OMeTAD, which demonstrated a maximum PCE of 12.58% under the same conditions. The PY2 and PY3 materials demonstrated slightly lower performance in device configuration, with relatively moderate PCEs of 10.21% and 10.82%, respectively, and slight hysteresis behavior (−0.01 and 0.02). The preliminary stability testing of PSCs is also described. The PY1-based device exhibited better stability than the device using Spiro-OMeTAD, which could be related to its slightly superior hydrophobic character preventing water diffusion into the perovskite layer.

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Section: Dft Calculationsmentioning

confidence: 95%

Section: Dft Calculationsmentioning

confidence: 99%

D-π-A-Type Pyrazolo[1,5-a]pyrimidine-Based Hole-Transporting Materials for Perovskite Solar Cells: Effect of the Functionalization Position

et al. 2022

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“…The meta-terphenyl structure has only two phenyl units conjugated due to the electronic nodal site at the meta-position. [13] Considering these facts and the results obtained for Pt-O and Pt-P, it suggests that the degree of 𝜋-conjugation of the D-𝜋-A ligand increases in the order of Pt-O < Pt-M < Pt-P. Furthermore, as shown in Figure 1c,f, the torsion angles between the phenyl linker and Pt-C phenyl in donorfree Pt-PhIMI are 40.3°and 42.5°, which are larger than that of the Pt-P and smaller than that of the Pt-O.…”

Section: Synthesis and Structural Characterizationmentioning

confidence: 99%

Efficient Solid‐State Emission Control by Positional Isomerism for Platinum(II) Complex with Donor–π–Acceptor Ligand

Kim

Chae

Ahn

et al. 2023

Advanced Optical Materials

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Square-planar platinum (Pt)(II) complexes have attracted considerable attention owing to their unique luminescent properties, and the development of facile methods to control them is very important. A series of Pt(II) complexes containing a donor-𝝅-acceptor (D-𝝅-A) isomer ligand (ortho-, meta-, and para-position; Pt-O, Pt-M, and Pt-P) is prepared to investigate the positional isomerism on the Pt(II) complex. In particular, the metal-to-ligand charge transfer and ligand intramolecular charge transfer characteristics are examined depending on the positional isomer and compared with the donor-free Pt(II) complex. All Pt(II) complexes observe slightly red-shifted emission within 10 nm in the order of Pt-O < Pt-M < Pt-P. Experimental data and theoretical calculations show that the Pt(II) complex lowest unoccupied molecular orbital energy level is controlled systematically by the donor position dependency. In particular, the small perturbation of the electronic state by positional isomerism in the single molecule induces significant phosphorescence color disparities of more than 82 nm in the solid-state emission spectra and aggregation-induced emission. The intriguing phosphorescent behavior is explained by the ligand-dependent macroscopic molecular array with the Hirshfeld analysis. Consequentially, this paper reports a facile emission control method by the D-𝝅-A ligand positional isomerism in the Pt(II) complex.

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“…On the one hand, porphyrin with the conjugated structure exhibit excellent optical and redox properties [6]. On the other hand, propeller-like triphenylamine is widely used as an electron donor [7].…”

Section: Introductionmentioning

confidence: 99%

Triphenylamine and porphyrin-based porous organic polymers for efficient visible-light photocatalysis

Duan²

2023

International Conference on Optoelectronic Materials and Devices (ICOMD 2022)

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The organic pollutants photodegradation is a highly efficient and environment-friendly approach for water treatment. Herein, two 3D imine-linked porphyrin-based porous organic polymers were synthesized via the reaction between porphyrin (tetraaminoporphyrin and copper tetraaminoporphyrin) and tri(4-formylbiphenyl) amine, named HTTP and CuTTP. Both of them exhibited high surface area, wide absorption range, and narrow bandgap. Interestingly, HTTP and CuTTP were used as photocatalysts for organic dye photodegradation. However, CuTTP was found to exhibit higher photocatalytic performance than HTTP, this indicates tuning the metal of porphyrin rings can affect the properties of porphyrin-based porous organic polymers.

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meta-Terphenyl linked donor–π–acceptor dyads: intramolecular charge transfer controlled by electron acceptor group tuning

Abstract: Dyads were prepared to understand the electronic effects of a meta-terphenyl linker according to the accepting ability change. The charge transfer properties in the ground/excited state are determined by accepting ability and/or steric hindrance.

Cited by 6 publications

References 77 publications

D-π-A-Type Pyrazolo[1,5-a]pyrimidine-Based Hole-Transporting Materials for Perovskite Solar Cells: Effect of the Functionalization Position

D-π-A-Type Pyrazolo[1,5-a]pyrimidine-Based Hole-Transporting Materials for Perovskite Solar Cells: Effect of the Functionalization Position

Efficient Solid‐State Emission Control by Positional Isomerism for Platinum(II) Complex with Donor–π–Acceptor Ligand

Triphenylamine and porphyrin-based porous organic polymers for efficient visible-light photocatalysis

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