Yuguo Ma

New cyclometalated transition-metal based photosensitizers for singlet oxygen generation and photodynamic therapy

The aim of this review article is to introduce recent studies on an emergent class of singlet oxygen photosensitizers of potential applications to the photodynamic therapy, with a primary focus on the cyclometalated transition-metal complexes. Singlet oxygen photosensitization performances of various cyclometalated Ir and Pt scaffolds are reviewed, and the general photophysical properties of relevant systems and the mechanisms of singlet oxygen production via photo-sensitization are also briefly discussed. Thus far, investigations of singlet oxygen sensitization by such Ir and Pt complexes are mainly carried out in organic solvents and under non-physiological conditions, while some research efforts have been made at examining the feasibility of applying pertinent cyclometalated complexes to photodynamic therapy.

Iridium-Based High-Sensitivity Oxygen Sensors and Photosensitizers with Ultralong Triplet Lifetimes

The photophysics of a series of bichromophoric molecules featuring an intramolecular triplet energy transfer between a triscyclometalated iridium(III) complex and covalently linked organic group are studied. By systematically varying the energy gap (0.1-0.3 eV) between the donor (metal complex) and acceptor (pyrene unit), reversible triplet energy transfer processes with equilibrium constant K ranging from ca. 500 to 40u202f000 are established. Unique photophysical consequences of such large K values are observed. Because of the highly imbalanced forward and backward energy transfer rates, triplet excitons dominantly populate the acceptor moiety in the steady state, giving rise to ultralong luminescence lifetimes up to 1-4 ms. Because the triscyclometalated Ir and triplet pyrene groups both impart relatively small nonradiative energy loss, decent phosphorescence quantum yields (Φ = 0.1-0.6) are attained in spite of the exceptionally prolonged excited states. By virtue of such precious combination of long-lived triplet state and high Φ, these bichromophoric molecules can serve as highly sensitive luminescent sensors for detecting trace amount of O2 and as potent photosensitizers for producing singlet oxygen even under low-oxygen content conditions.

Triplet-Triplet Annihilation Photon Upconversion in Polymer Thin Film: Sensitizer Design.

Efficient visible-to-UV photon upconversion via triplet-triplet annihilation (TTA) is accomplished in polyurethane (PU) films by developing new, powerful photosensitizers fully functional in the solid-state matrix. These rationally designed triplet sensitizers feature a bichromophoric scaffold comprising a tris-cyclometalated iridium(III) complex covalently tethered to a suitable organic small molecule. The very rapid intramolecular triplet energy transfer from the former to the latter is pivotal for achieving the potent sensitizing ability, because this process out-competes the radiative and nonradiative decays inherent to the metal complex and produces long-lived triplet excitons localized with the acceptor moiety readily available for intermolecular transfer and TTA. Nonetheless, compared to the solution state, the molecular diffusion is greatly limited in solid matrices, which even creates difficulty for the Dexter-type intramolecular energy transfer. This is proven by the experimental results showing that the sensitizing performance of the bichromophoric molecules strongly depends on the spatial distance separating the donor (D) and acceptor (A) units and that incorporating a longer linker between the D and A evidently curbs the TTA upconversion efficiency in PU films. Using a rationally optimized sensitizer structure in combination with 2,7-di-tert-butylpyrene as the annihilator/emitter, the doped polyurethane (PU) films demonstrate effective visible-to-UV upconverted emission signal under noncoherent-light irradiation, attaining an upconversion quantum yield of 2.6%. Such quantum efficiency is the highest value so far reported for the visible-to-UV TTA systems in solid matrices.

Enhanced Triplet Sensitizing Ability of an Iridium Complex by Intramolecular Energy-transfer Mechanism

The photodynamic properties involving both intra- and intermolecular triplet energy transfers (ET) of a bichromophoric photosensitizer having a tris-cyclometalated Ir(III) tethered with a pyrene derivative are studied. Due to the triplet energy gap of the two chromophores, a reversible intramolecular triplet ET equilibrium is quickly established upon photoexcitation, with the triplet exciton mainly residing on the acceptor side in the photostationary state. By virtue of the very small decay rate of triplet pyrene, a considerably extended triplet lifetime (2 ms) is observed. Next, the intermolecular triplet-triplet ET properties are investigated. Using steady-state and time-resolved spectroscopy, the ET rate constants from the Ir complex and pyrene unit in the sensitizer to an external triplet acceptor (unattached, free pyrene derivative) in solution are found to be around 109 s-1 and 108 M -1 s-1, respectively. In spite of a lower ET rate constant, the tethered pyrene serves as the main intermolecular ET channel because of the large, favorable intramolecular ET equilibrium ( K ∼ 103). Importantly, this cascade ET process, from Ir complex to linked pyrene, and then to free pyrene, offers an overall improved ET efficiency than a direct ET from Ir complex to free pyrene, by virtue of the much smaller spontaneous decay rate compared to that of the metal complex. Finally, the more efficient ET ability is demonstrated experimentally by applying the molecule as sensitizer in a triplet-triplet annihilation upconversion. The bichromophoric sensitizer achieved upconverted emission intensity 5 times higher than a monochromophoric Ir-complex analogue.

Synthesis, solvent-dependent emission and two-photon absorption of a triangular –[D–π–A]3– macrocycle

A large triangular arylene–ethynylene macrocycle featuring unique circularly arranged –[D–π–A]3– electronic characteristics is designed and synthesized. The shape-persistent π-conjugated backbone is composed of alternating electron-rich dialkoxyphenanthrene and electron-deficient dicyanodibenzo[f,h]quinoxaline units, connected by ethynylene linkers. The synthesis of such a special macrocyclic molecule is realized by employing a post-cyclization functional group installation strategy. The absorption and emission spectra of the macrocycle are found sensitively dependent on the solvent polarity. By virtue of a conjugated π-scaffold and a cyclic –[D–π–A]3– motif, evident two-photon absorption (2PA) and two-photon excitation fluorescence properties are exhibited, with a 2PA cross section maximum of 3 × 103 GM determined by the Z-scan method.