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Photophysical and Photobiological Properties of Dinuclear Iridium(III) Bis-tridentate Complexes

Journal Article · · Inorganic Chemistry
 [1];  [2];  [1];  [3];  [3];  [2];  [1];  [4];  [1]
  1. North Dakota State Univ., Fargo, ND (United States)
  2. Acadia Univ., Wolfville, NS (Canada)
  3. Univ. of North Carolina, Greensboro, NC (United States)
  4. Acadia Univ., Wolfville, NS (Canada); Univ. of North Carolina, Greensboro, NC (United States)

A series of cationic dinuclear iridium(III) complexes (Ir1–Ir5) bearing terpyridine-capped fluorenyl bridging ligands and different polypyridyl or cyclometalating terminal tridentate ligands were synthesized, characterized, and evaluated for their photophysical and photobiological activities. The influence of the bridging and terminal ligands on the photophysical properties of the complexes was investigated by UV–vis absorption, emission, and transient absorption spectroscopy and simulated by TDDFT calculations. All of the complexes displayed strong bridging-ligand localized visible 1π,π* absorption and red- or near-infrared phosphorescence as well as broad triplet excited-state absorption across both visible and NIR wavelengths. These triplet states were assigned as predominantly 3π,π* for Ir1 (τ = 3.1 μs) and Ir4 (τ = 48 μs) and 3CT (charge transfer) for Ir2, Ir3, and Ir5 (τ = 1.7–2.7 μs). Complexes Ir1–Ir5 acted as in vitro photodynamic therapy (PDT) agents toward human SK-MEL-28 melanoma cells when activated with visible light, with submicromolar photocytotoxicity and phototherapeutic indices ranging from 20 to almost 300. The in vitro PDT effects with visible light did not correlate with singlet oxygen (1O2) quantum yields or DNA photocleaving capacity probed under cell-free conditions. All of the Ir(III) complexes phosphoresced brightly when associated with compromised cells (with or without light treatment) and exhibited photoactivated cellular uptake, highlighting the theranostic potential of this new class of Ir(III) complex photosensitizers.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543620
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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A Highly Luminescent Tetrahydrocurcumin Ir III Complex with Remarkable Photoactivated Anticancer Activity journal April 2019
Monocationic Iridium(III) Complexes with Far-Red Charge-Transfer Absorption and Near-IR Emission: Synthesis, Photophysics, and Reverse Saturable Absorption: Monocationic Iridium(III) Complexes with Far-Red Charge-Transfer Absorption and Near-IR Emission: Synthesis, Photophysics, and Reverse Saturable Absor journal April 2019
Proximity effects on the phosphorescent properties of dinuclear salicylaldiminato cyclometalated iridium(III) complexes linked with polymethylene spacers journal December 2019
Dinuclear metal complexes: multifunctional properties and applications journal January 2020
Multinuclear Ru( ii ) and Ir( iii ) decorated tetraphenylporphyrins as efficient PDT agents journal January 2019
Heteroleptic cationic iridium( iii ) complexes bearing phenanthroline derivatives with extended π-conjugation as potential broadband reverse saturable absorbers journal January 2020
Solvent-induced aggregation based on a heteroleptic Ir( iii ) complex via hydrogen bonds journal January 2019

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