Synthesis, structures and luminescence properties of N^C^N-coordinated platinum(II) complexes based on an anthracene core: A red shift and a twist

Wood, Emily; Gildea, Louise F.; Yufit, Dmitry S.; Williams, John A.

doi:10.1016/j.poly.2021.115401

Cited by 12 publications

(8 citation statements)

References 75 publications

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“…The results of these analyses were in good agreement with the broad emission spectra, the almost unchanged variable-temperature PL spectra, the absence of significant solvatochromism, and the low quantum efficiencies of PtYK1 and PtYK2. In addition, many other Pt(II) complexes reported in the literature showed a short vibrational progression involving ligand-centered characters, as typically observed for the tridentate Pt(II) complexes with large π-conjugated ligands developed by the Williams, and Yersin groups. − These results also reveal that the NHC carbene moiety plays a critical role in their photophysical properties, and the emission spectra of the Pt(II) complexes are strongly dependent on the excited-state properties and ligand structures.…”

Section: Resultssupporting

confidence: 52%

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible ³MLCT Character

Li,

Liu,

et al. 2024

Inorg. Chem.

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Two novel six-membered perimidocarbene (PIC)-based tetradentate Pt(II) complexes were designed and successfully synthesized. Systematical experimental and theoretical studies suggest that the PIC moiety greatly affects the frontier orbitals, as well as the photophysical and excited-state properties of the Pt(II) complexes. PtYK2 has a broad emission spectrum peaking at 576 nm with a shoulder band at 620 nm, along with a full width at half-maximum (FWHM) value of 100.0 nm at 77 K in 2-MeTHF; however, the emission spectrum is slightly red-shifted with a dominant peak at 610 nm and a FWHM value of 125.0 nm at room temperature in a poly(methyl methacrylate) (PMMA) film. Time-dependent-density functional theory and natural transition orbital analyses reveal that PtYK2 has a 3LC (3πPIC* → πPIC)-dominated character with an unexpectedly negligible contribution of 3MLCT transition (0.68%) in the T1 state, which results in a broad emission spectrum and a relatively low quantum efficiency of 7.4% in the PMMA film.

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Section: Resultssupporting

confidence: 52%

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible ³MLCT Character

Li,

Liu,

et al. 2024

Inorg. Chem.

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“… a dqb Me,Me = 4,6-dimethyl-1,3-di(8-quinolinyl)benzene. Data from ref . b Data from ref . c X = coordinating atom of the trans coligand (X = Cl in each case except the acetylido and pyridine complexes for which X = C and N respectively). …”

Section: Results and Discussionmentioning

confidence: 99%

“…A similar trend is well-documented for pseudo-octahedral Ru(II) complexes containing tridentate ligands. , Yet, for cyclometalated N ∧ C – ∧ N-coordinated Pt(II) emitters, increasing chelate ring size to improve the bite angle proved to have the opposite effect: compared with Pt(dpyb)Cl which boasts five-membered chelate rings, Pt(dqb)Cl (dqb = 1,3-di(8-quinolinyl)benzene) exhibits a significantly lower radiative rate constant ( k r = 1100 versus 83 000 s –1 ; attributed to diminished metal participation in the excited state) and hence a much smaller quantum yield (0.016) . Similarly, a tridentate ligand that binds via 6-membered chelate rings using 7- N -substituted azaindole moieties was found to be nonemissive, as was the N ∧ C –∧ N -coordinated Pt(II) complex of 1,8-bis(2-pyridyl)anthracene despite an ostensibly more favorable ligand geometry at the metal center in both cases.…”

Section: Introductionmentioning

confidence: 96%

Brightly Luminescent Platinum Complexes of N^∧C^–^∧N Ligands Forming Six-Membered Chelate Rings: Offsetting Deleterious Ring Size Effects Using Site-Selective Benzannulation

et al. 2021

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Brightly emissive platinum(II) complexes (λemission,max = 607–612 nm) of the type R LPtCl are reported, where R L is a cyclometalated N∧C–∧N-coordinating ligand derived from 1,3-di(2-trifluoromethyl-4-phenanthridinyl)benzene ( CF3 LH) or 1,3-di(2-tert-butyl-4-phenanthridinyl)benzene ( t Bu LH). Metathesis of the chlorido ligand can be achieved under mild conditions, enabling isolation of ionic compounds with the formula [ CF3 LPtL′]PF6 where L′ = pyridine or (4-dimethylamino)pyridine (DMAP), as well as the charge-neutral species t Bu LPt(CCC6H4tBu) (CCC6H4tBu = 4-tert-butylphenylacetylido). Compared with N∧N∧N-ligated Pt(II) complexes that form 5-membered chelates, these compounds all contain 6-membered rings. Expanding the chelate ring size from 5 to 6 has been previously demonstrated to enhance emission in some N∧N∧N-coordinated Pt(II) speciesfor example, in complexes of 2,6-di(8-quinolinyl)pyridine vs those of 2,2′:6′,2″-terpyridinebut in related N∧C–∧N-coordinated species, luminescence quantum yields are significantly lower for the 6-membered chelate ring complexes. Here, we demonstrate that site-selective benzannulation of the quinolinyl side-arms can offset the deleterious effect of changing the chelate ring-size and boost photophysical properties such as the quantum yield. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations suggest that benzannulation counterintuitively destabilizes the emissive triplet states compared to the smaller π-system, with the “imine-bridged biphenyl” form of the phenanthridinyl arm helping to buffer against larger molecular distortions, enhancing photoluminescence quantum yields up to 0.09 ± 0.02. The spontaneous formation under aerated conditions of a Pt(IV) derivative ( CF3 LPtCl3) is also reported, together with its molecular structure in the solid state.

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“…On the other hand, platinum(II) transition‐metal complexes having extended π‐conjugation can be used as a key to induce the π‐π stacking interactions between square‐plane dimers to obtain longer wavelength emissions [75]. The lowest energy excited state of the platinum(II) compounds are generally characterized by a metal‐to‐ligand‐charge transfer (MLCT) and/or ligand‐to‐ligand‐charge transfer (LLCT) as well as ligand‐centered (LC) triplet character in many examples [76].…”

Section: Introductionmentioning

confidence: 99%

Organic light‐emitting diode behaviors of some synthesized platinum(II)‐based complexes

Üngördü

2023

Int J of Quantum Chemistry

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Organic light‐emitting light diodes (OLEDs) have been increasingly used in displays, replacing liquid‐crystal displays (LCD) and light‐emitting diodes (LEDs) panels. The increase in commercial use of OLED has led to the search for OLED with high performance. For that reason, the OLED properties of monomers and dimers of some synthesized platinum(II)‐based complexes were estimated by using different computational chemistry tools with different codes. The electron/hole reorganization energies, the adiabatic/vertical ionization potentials, the adiabatic/vertical electron affinities, the chemical hardness values, the dipole moments, the frontier orbital shapes/energy levels, the energy gaps, the emission wavelengths, spin‐orbit matrix elements, the rates of reverse intersystem crossing and intersystem crossing of the investigated complexes were determined. From the theoretically obtained data, it was found that Pt(hppz)2 and Pt(fppz)2 complexes can be used as electron transfer material. Furthermore, it was stated that Pt(f2bipz)(bpy) is both electron‐blocking layer and hole blocking layer materials. Moreover, it was noted that that PtOEP complex can be utilized as a good electron injection layer and hole injection layer material. Addition to these, it was emphasized that that Pt(f2bipz)(bpy) can be considered as a good candidate for near infrared organic light emitting diodes and thermal activated delayed fluorescent organic light emitting diodes. In light of computational chemistry, it should be expected that the study will provide a great contribution to studies related to organic light emitting diodes.

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Synthesis, structures and luminescence properties of N^C^N-coordinated platinum(II) complexes based on an anthracene core: A red shift and a twist

Cited by 12 publications

References 75 publications

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible ³MLCT Character

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible ³MLCT Character

Brightly Luminescent Platinum Complexes of N^∧C^–^∧N Ligands Forming Six-Membered Chelate Rings: Offsetting Deleterious Ring Size Effects Using Site-Selective Benzannulation

Organic light‐emitting diode behaviors of some synthesized platinum(II)‐based complexes

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Synthesis, structures and luminescence properties of N^C^N-coordinated platinum(II) complexes based on an anthracene core: A red shift and a twist

Cited by 12 publications

References 75 publications

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible 3MLCT Character

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible 3MLCT Character

Brightly Luminescent Platinum Complexes of N∧C–∧N Ligands Forming Six-Membered Chelate Rings: Offsetting Deleterious Ring Size Effects Using Site-Selective Benzannulation

Organic light‐emitting diode behaviors of some synthesized platinum(II)‐based complexes

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Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible ³MLCT Character

Perimidocarbene-Based Tetradentate Platinum(II) Complexes with an Unexpectedly Negligible ³MLCT Character

Brightly Luminescent Platinum Complexes of N^∧C^–^∧N Ligands Forming Six-Membered Chelate Rings: Offsetting Deleterious Ring Size Effects Using Site-Selective Benzannulation