The Utilization of <i>Para</i>‐Substituted Triphenylphosphine Derivatives to Synthesize Highly Emissive Cyclometalated Platinum(II) Complexes

Shahsavari, Hamid R.; Chamyani, Samira; Hu, Jiyun; Aghakhanpour, Reza Babadi; Rheingold, Arnold L.; Paziresh, Sareh; Rahal, Dania; Tsuji, Miu; Momand, Bilal; Beyzavi, Hudson

doi:10.1002/ejic.202100732

Cited by 7 publications

(20 citation statements)

References 71 publications

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“…Scheme depicts the syntheses of the complexes [PtMe(dfppy)(L)], L = py, 1 ; 2-NH 2 -py, 2 ; 3-NH 2 -py, 3 ; 4-NH 2 -py, 4 ; and [Pt( p -MeC 6 H 4 )(dfppy)(L)], L = py, 5 ; 2-NH 2 -py, 6 ; 3-NH 2 -py, 7 ; and 4-NH 2 -py, 8 . The methyl ( 1–4 ) and aryl ( 5–8 ) compounds can be prepared through the reaction of the known precursor complexes [PtMe(dfppy)(SMe 2 )], A , and [Pt( p -MeC 6 H 4 )(dfppy)(SMe 2 )], B , with pyridine and aminopyridine derivatives at room temperature, respectively. In addition to these complexes, the ppy counterpart of 6 , that is, complex [Pt( p -MeC 6 H 4 )(ppy)(2-NH 2 py)], 6′ , was prepared for a photophysical comparison.…”

Section: Results and Discussionmentioning

confidence: 95%

“…The ĈN bite angles for 4 and 8 are 80.84(3) and 80.69(5)°, respectively. These values are usual for this kind of ĈN ligands, which impose a substantial strain on the structures. , Crystal packings (Figures S14 and S15) show several different C–F....H–C contacts. Additionally, a NH 2 ...π ( p -MeC 6 H 4 ) interaction is found for 8 .…”

Section: Results and Discussionmentioning

confidence: 99%

“…The complexes [PtMe(dfppy)(SMe 2 )], A , and [Pt( p -MeC 6 H 4 )(dfppy)(SMe 2 )], B , [Pt( p -MeC 6 H 4 )(ppy)(SMe 2 )], C , were prepared using the previously published methods in the literature. The NMR labeling is depicted in Scheme for the chemical shift assignments.…”

Section: Methodsmentioning

confidence: 99%

“…Five probable arrangements can be considered in these complexes, that is, L ̂X, 38,39 L ̂L, 40,41 L/X, 42,43 L/L, 44,45 and X/X. 46,47 In this nomenclature, L describes neutral ligands with an N, P, or C donor atom, while X represents anionic ligands such as halides, alkyls, or aryl carbanions (Me, p-MeC 49 with pyridine and aminopyridine derivatives at room temperature, respectively. In addition to these complexes, the ppy counterpart of 6, that is, complex [Pt(p-MeC 6 H 4 )(ppy)(2-NH 2 py)], 6′, was prepared for a photophysical comparison.…”

Section: ■ Introductionmentioning

confidence: 99%

“…DFT and TD-DFT calculations support the fact that the characters of emissive states in 1−4 and 5−8 mainly originated from mixed 3 π−π* (dfppy)/ 3 MLCT and 3 L″LCT/ 3 MLCT (L = dfppy, L″ = p-MeC 6 H 4 ), respectively.■ EXPERIMENTAL SECTIONGeneral Procedures and Materials. The complexes [PtMe-(dfppy)(SMe 2 )], A,48 and [Pt(p-MeC 6 H 4 )(dfppy)(SMe 2 )], B,49 [Pt(p-MeC 6 H 4 )(ppy)(SMe 2 )], C,52 were prepared using the previously published methods in the literature. The NMR labeling is depicted in Scheme 2 for the chemical shift assignments.…”

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Fine-Tuning of Luminescence Properties of Cyclometalated Platinum(II) Complexes via Aminopyridine Derivatives

et al. 2022

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The present work describes two families of cycloplatinated(II) complexes [PtR(dfppy)(L)], dfppy = 2-(2,4-difluorophenyl)pyridinate, R = Me and p-MeC 6 H 4 and L = pyridine, py, and aminopyridine derivatives, x-NH 2 -py, x = 2, 3, and 4. The complexes show similar UV−vis spectra possessing intense bands in the 250−400 region, which are assigned as π−π* transitions and mixed metal-to-ligand charge transfer (MLCT)/π−π*. The MLCTs are observed as weak broad bands in the range 400−500 nm. Meanwhile, structured emission bands are observed for the complexes in the range 450−600 nm with quantum efficiencies up to 0.7, wherein the p-MeC 6 H 4 derivatives show higher emission strengths compared to their Me-containing counterparts. Moreover, the NH 2 position on the pyridine significantly affects the emission efficiency of the Me derivatives and conversely does not show a large impact on the emission intensity of the p-MeC 6 H 4 -containing complexes. DFT and TD-DFT calculations reveal that 3 π−π* (dfppy)/ 3 MLCT are responsible for the emissions in the Me complexes. However, in the p-MeC 6 H 4 complexes, the emissions originate from 3 L″LCT and 3 MLCT (L = dfppy, L″ = p-MeC 6 H 4 ).

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Section: Results and Discussionmentioning

confidence: 95%

Section: Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Fine-Tuning of Luminescence Properties of Cyclometalated Platinum(II) Complexes via Aminopyridine Derivatives

et al. 2022

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Reaction Pathways of Diplatinum Complexes Bearing a Phenylpropene‐ Derived π/σ‐Chelator with Weak/Strong σ‐Donor Neutral Ligands

et al. 2022

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The reaction of complexes [Pt(μ-Cl)(arylolefin)] 2 with various either weak σ-donor L N,S,O ligands or strong σ-donor NHCs ligands results in [PtCl(arylolefin)(L N,S,O )] with L N,S,O in a cis position to the C=C group (series A) or [PtCl(arylolefin)(NHC)] with NHC in a trans position to the C=C group (series B), respectively. The reaction directions are decided by the nature of the reactants, and not by the reaction conditions. Analyses of NMR spectra, XRD and DFT results indicate that the formation of series B is strongly dominated by electronic properties, while steric factors direct the reaction to form series A. The chemical shifts of ethylenic protons and carbons as well as the values of 2 J PtH , 3 J PtH for the allyl protons and the 3 J PtH value for H6 in the aryl group are unambiguously different for series A and series B. In addition, one complex [Pt(μ-Cl)(EtEug)] 2 and five complexes [PtCl(arylolefin)(NHC)] have been characterized by single crystal XRD.

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Luminescent Anionic Cyclometalated Organoplatinum (II) Complexes with Terminal and Bridging Cyanide Ligand: Structural and Photophysical Properties

et al. 2023

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We present the synthesis and characterization of two series of mononuclear heteroleptic anionic cycloplatinated(II) complexes featuring terminal cyanide ligand Q+[Pt(C^N)(p-MeC6H4)(CN)]− [C^N = benzoquinolate (bzq), Q+ = K+ 1 and NBu4 + 4; 2-phenylpyridinate (ppy), Q+ = K+ 2 and NBu4 + 5 and 2-(2,4- difluorophenyl)pyridinate (dfppy), Q+ = K+ 3 and NBu4 + 6] and a series of symmetrical binuclear complexes (NBu4)[Pt2(C^N)2(p-MeC6H4)2(μ-CN)] (C^N = bzq 7, ppy 8, dfppy 9). Compounds 5, 6, and 7–9 were further determined by single-crystal X-ray diffraction. There are no apparent intermolecular Pt···Pt interactions owing to the presence of bulky NBu4 + counterion. Slow crystallization of K[Pt(ppy)(p-MeC6H4)(CN)] 2 in acetone/hexane evolves with formation of yellow crystals, which were identified by single-crystal X-ray diffraction methods as the salt complex {[Pt(ppy)(p-MeC6H4)(CN)]2K3(OCMe2)4(μ-OCMe2)2}[Pt(ppy)(p-MeC6H4)(μ-CN)Pt(ppy)(p-MeC6H4)]·2acetone (10), featuring the binuclear anionic unit 8– neutralized by an hybrid inorganic–organometallic coordination polymer {[Pt(ppy)(p-MeC6H4)(CN)]2K3(OCMe2)4(μ-OCMe2)2}+. The photophysical properties of all compounds were recorded in powder, polystyrene film, and solution states with a quantum yield up to 21% for 9 in the solid state. All complexes displayed bright emission in rigid media, and for the interpretation of their absorption and emission properties, density functional theory (DFT) and time-dependent DFT calculations were applied.

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The Utilization of Para‐Substituted Triphenylphosphine Derivatives to Synthesize Highly Emissive Cyclometalated Platinum(II) Complexes

Cited by 7 publications

References 71 publications

Fine-Tuning of Luminescence Properties of Cyclometalated Platinum(II) Complexes via Aminopyridine Derivatives

Fine-Tuning of Luminescence Properties of Cyclometalated Platinum(II) Complexes via Aminopyridine Derivatives

Reaction Pathways of Diplatinum Complexes Bearing a Phenylpropene‐ Derived π/σ‐Chelator with Weak/Strong σ‐Donor Neutral Ligands

Luminescent Anionic Cyclometalated Organoplatinum (II) Complexes with Terminal and Bridging Cyanide Ligand: Structural and Photophysical Properties

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