Dataset Information

Polymorphism and Mechanochromism in 2-Phenylbenzothiazole Cyclometalated Pt^II Complexes with Chelating N^∧O Ligands.

ABSTRACT: New cyclometalated Pt^II complexes with 2-phenylbenzothiazole (pbt) and two different picolinate ligands [Pt(pbt)(R-pic-κN,O)] (R = H (1), OH (2)) were prepared. In contrast to 1, the OH substituent group on 2 allows modulation of the packing in the solid state through donor-acceptor H-bonding interactions with the CH₂Cl₂ solvent. Thus, three pseudopolymorphs of 2 with different aggregation degrees were isolated, including yellow 2-Y, orange-red 2-R (2·0.5CH₂Cl₂) and black 2-B (2·0.75CH₂Cl₂) with emissions at 540, 656, and 740 nm, respectively, in the solid state at 298 K. 2-R and 2-B can be transformed to the pristine solid 2. Studies of their crystal structures show that 1 and 2-Y stack in columns with only π···π stacking interactions, whereas 2-R displays strong aggregated 1D infinite chains based on Pt···Pt and π···π stacking interactions, consistent with the colors and the photophysical properties, measured in several media. Interestingly, 1 and 2 exhibit reversible mechanochromic behavior with high contrast in the color and color emission upon mechanical grinding due to a phase transition between a crystalline and an amorphous state, as confirmed by powder X-ray diffraction (PXRD) studies. Theoretical calculations indicate that Pt···Pt contacts are more relevant in the trimers and tetramers than in the dimers, particularly in their T₁ states, associated with a change from a ³IL/³MLCT transition in the monomer to ³MM(L+L')CT in the oligomers. Noncovalent interaction (NCI) theoretical studies indicate that the π···π stacking among chelates also exerts a strong influence in the metal-metal-to-ligand charge transfer transition character.

SUBMITTER: Gomez de Segura D

PROVIDER: S-EPMC9749027 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

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Polymorphism and Mechanochromism in 2-Phenylbenzothiazole Cyclometalated PtII Complexes with Chelating N∧O Ligands.

Gómez de Segura David D Lalinde Elena E Moreno M Teresa MT

Inorganic chemistry 20221128 49

New cyclometalated PtII complexes with 2-phenylbenzothiazole (pbt) and two different picolinate ligands [Pt(pbt)(R-pic-κN,O)] (R = H (1), OH (2)) were prepared. In contrast to 1, the OH substituent group on 2 allows modulation of the packing in the solid state through donor-acceptor H-bonding interactions with the CH2Cl2 solvent. Thus, three pseudopolymorphs of 2 with different aggregation degrees were isolated, including ...[more]

PMID: 36442499

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Project description:The incorporation of a trifluoromethyl group into an existing scaffold can provide an effective strategy for designing new drugs and agrochemicals. Among the numerous approaches to trifluoromethylation, radical trifluoromethylation mediated by visible light-driven photoredox catalysis has gathered significant interest as it offers unique opportunities for circumventing the drawbacks encountered in conventional methods. A limited understanding of the mechanism and molecular parameters that control the catalytic actions has hampered the full utilization of photoredox catalysis reactions. To address this challenge, we evaluated and investigated the photoredox catalytic trifluoromethylation reaction using a series of cyclometalated Pt(ii) complexes with systematically varied ligand structures. The Pt(ii) complexes were capable of catalyzing the trifluoromethylation of non-prefunctionalized alkenes and heteroarenes in the presence of CF3I under visible light irradiation. The high excited-state redox potentials of the complexes permitted oxidative quenching during the cycle, whereas reductive quenching was forbidden. Spectroscopic measurements, including time-resolved photoluminescence and laser flash photolysis, were performed to identify the catalytic intermediates and directly monitor their conversions. The mechanistic studies provide compelling evidence that the catalytic cycle selects the oxidative quenching pathway. We also found that electron transfer during each step of the cycle strictly adhered to the Marcus normal region behaviors. The results are fully supported by additional experiments, including photoinduced ESR spectroscopy, spectroelectrochemical measurements, and quantum chemical calculations based on time-dependent density functional theory. Finally, quantum yields exceeding 100% strongly suggest that radical propagation significantly contributes to the catalytic trifluoromethylation reaction. These findings establish molecular strategies for designing trifluoromethyl sources and catalysts in an effort to enhance catalysis performance.

Project description:In a series of Pt(II) complexes [Pt(dba)(L)] containing the very rigid, dianionic, bis-cyclometalating, tridentate C^N^C2- heterocyclic ligand dba2- (H2dba = dibenzo[c,h]acridine), the coligand (ancillary ligand) L = dmso, PPh3, CNtBu and Me2Imd (N,N'-dimethylimidazolydene) was varied in order to improve its luminescence properties. Beginning with the previously reported dmso complex, we synthesized the PPh3, CNtBu and Me2Imd derivatives and characterized them by elemental analysis, 1H (and 31P) NMR spectroscopy and MS. Cyclic voltammetry showed partially reversible reduction waves ranging between -1.89 and -2.10 V and increasing along the series Me2Imd < dmso ≈ PPh3 < CNtBu. With irreversible oxidation waves ranging between 0.55 (L = Me2Imd) and 1.00 V (dmso), the electrochemical gaps range between 2.65 and 2.91 eV while increasing along the series Me2Imd < CNtBu < PPh3 < dmso. All four complexes show in part vibrationally structured long-wavelength absorption bands peaking at around 530 nm. TD-DFT calculated spectra agree quite well with the experimental spectra, with only a slight redshift. The photoluminescence spectra of all four compounds are very similar. In fluid solution at 298 K, they show broad, only partially structured bands, with maxima at around 590 nm, while in frozen glassy matrices at 77 K, slightly blue-shifted (~580 nm) bands with clear vibronic progressions were found. The photoluminescence quantum yields ΦL ranged between 0.04 and 0.24, at 298 K, and between 0.80 and 0.90 at 77 K. The lifetimes τ at 298 K ranged between 60 and 14040 ns in Ar-purged solutions and increased from 17 to 43 µs at 77 K. The TD-DFT calculated emission spectra are in excellent agreement with the experimental findings. In terms of high ΦL and long τ, the dmso and PPh3 complexes outperform the CNtBu and Me2Imd derivatives. This is remarkable in view of the higher ligand strength of Me2Imd, compared with all other coligands, as concluded from the electrochemical data.

Dataset Information

Polymorphism and Mechanochromism in 2-Phenylbenzothiazole Cyclometalated Pt^II Complexes with Chelating N^∧O Ligands.

Publications

Polymorphism and Mechanochromism in 2-Phenylbenzothiazole Cyclometalated Pt<sup>II</sup> Complexes with Chelating N<sup>∧</sup>O Ligands.

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