Abstract
Organic ligands comprising thiophene ring(s) afford complexes of transition metals, such as Pt(II) and Ir(III), with photoluminescence readily tunable via ligand modifications. In this work we demonstrate the targeted design of a N<^>C-C<^>N type ditopic ligand with a central thiophene ring as the cyclometalating core and variation of the nuclearity of the complex to fine-tune the photophysical ...
Abstract
Organic ligands comprising thiophene ring(s) afford complexes of transition metals, such as Pt(II) and Ir(III), with photoluminescence readily tunable via ligand modifications. In this work we demonstrate the targeted design of a N<^>C-C<^>N type ditopic ligand with a central thiophene ring as the cyclometalating core and variation of the nuclearity of the complex to fine-tune the photophysical properties of the material. The mononuclear complex Pt-1 shows red T-1 -> S-0 phosphorescence with the emission maximum at lambda = 660 nm. The dinuclear complex Pt-2 shows near infrared (NIR) T-1 -> S-0 phosphorescence peaking at lambda = 710 nm. In both cases the phosphorescence is quenched by molecular oxygen generating singlet oxygen molecules with high efficiencies of phi(Delta) approximate to 83% (Pt-1) and phi(Delta)approximate to 70% (Pt-2, respectively) in air-equilibrated CH2Cl2 solutions under ambient conditions. The red phosphorescence of Pt-1 is accompanied by green S-1 -> S-0 fluorescence with the maximum at lambda = 495 nm. This makes Pt-1 a dual emissive material with two emissions stemming from a single chromophore moiety. Transient absorption studies revealed a relatively low rate of ISC from the S-1 state to the triplet manifold with a time constant tau(ISC) of about 4 ps. The slow ISC in Pt-1 is rationalized by a specific electronic structure with a relatively large energy gap Delta E(S-1 -> T-1) approximate to 0.63 eV and the higher triplet state T-2 being higher in energy than the singlet state S-1. In dinuclear Pt-2, state T-2 lies below S-1 opening fast T-2 -> S-1 ISC paths with a time constant tau of only approximate to 0.13 ps. The unique dual emission of Pt-1 was beneficial for its imaging in HeLa cells as it enabled switching between green fluorescence and red phosphorescence channels of detection in the time-span of the single confocal luminescence microscopy experiment. Pt-1 represents a prototype of new theranostic agents combining cytotoxic activity with a unique dual wavelength mode of detection.
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