The synthesis, photophysics, reverse saturable absorption, and photodynamic therapeutic effect of six cationic biscyclometalated Ir(iii) complexes (1-6) with extended π-conjugation on the diimine ligand and/or the cyclometalating ligands are reported in this paper. All complexes possess ligand-localized π,π* absorption bands below 400 nm and charge-transfer absorption bands above 400 nm. They are all emissive in the 500-800 nm range in deoxygenated solutions at room temperature. All complexes exhibit strong and broad triplet excited-state absorption at 430-800 nm, and thus strong reverse saturable absorption for ns laser pulses at 532 nm. Complexes 1-4 are strong reverse saturable absorbers at 532 nm, while complex 6 could be a good candidate as a broadband reverse saturable absorber at 500-850 nm. The degree of π-conjugation of the diimine ligand mainly influences theπ,π* transitions in their UV-vis absorption spectra, while the degree of π-conjugation of the cyclometalating ligand primarily affects the nature and energies of the lowest singlet and emitting triplet excited states. However, the lowest-energy triplet excited states for complexes 3-6 that contain the same benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (dppn) diimine ligand but different cyclometalating ligands remain the same as the dppn ligand-localized π,π* state, which gives rise to the long-lived, strong excited-state absorption in the visible to the near-IR region. All of the complexes exhibit a photodynamic therapeutic effect upon visible or red light activation, with complex 6 possessing the largest phototherapeutic index reported to date (>400) for an Ir(iii) complex. Interactions with biological targets such as DNA suggest that a novel mechanism of action may be at play for the photosensitizing effect. These Ir(iii) complexes also produce strong intracellular luminescence that highlights their potential as theranostic agents.
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 π,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 predominantlyπ,π* for Ir1 (τ = 3.1 μs) and Ir4 (τ = 48 μs) and CT (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 (O) 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.
Extending π-conjugation of the diimine ligand (N^N ligand) via benzannulation is a common way to tune the absorption and emission energies of cationic iridium(III) complexes. However, it can cause either a red- or blue-shift of the absorption and emission bands depending on the site of benzannulation. To understand the mechanism of changes in optical transitions upon benzannulation on the diimine ligand, a series of new cationic iridium(III) complexes [Ir(dppi)(N^N)]PF (1-6) (where dppi =1,2-diphenylpyreno[4,5-d]imidazole; N^N = 2-(pyridin-2-yl)quinoline (1), 2-(pyridin-2-yl)[7,8]benzoquinoline (2), 2,2'-bisquinoline (3), 2-(quinolin-2-yl)[7,8]benzoquinoline (4), 2-(pyridin-2-yl)[6,7]benzoquinoline (5), 2-(quinolin-2-yl)[6,7]benzoquinoline (6)) containing diimine ligand with varied degrees of π-conjugation via benzannulation at different sites of the 2-(pyridin-2-yl)quinoline ligand were synthesized. Experimental results and density functional theory (DFT) calculations revealed that benzannulation at the 6,7-position of quinoline and/or the 5',6'-position of pyridine (3, 5, and 6) induced red-shifts in their absorption and emission bands with respect to the parent complex 1; while benzannulation at the 7,8-position of quinoline resulted in blue-shifts (2 vs 1 and 4 vs 3). This phenomenon was rationalized by the symmetry of the frontier molecular orbitals at the site of benzannulation, which stabilized or destabilized the lowest unoccupied molecular orbital (LUMO) upon interactions with 1,3-butadiene, while the energy of the highest occupied molecular orbital (HOMO) remained nearly the same. This discovery would enable a rational design of organic or organometallic compounds that have predetermined absorption and emission energies.
To understand the effects of the terminal substituent at the diimine ligand on the photophysics of heteroleptic cationic Ir(III) complexes and to obtain Ir(III) complexes with extended ground-state absorption to the near-IR region while retaining the long-lived and broadly absorbing triplet excited state, we synthesized three heteroleptic cationic iridium(III) complexes bearing cyclometalating 1-phenylisoquinoline (C^N) ligands and substituted 6,6'-bis(7-R-fluoren-2-yl)-2,2'-biquinoline (N^N) ligand (R = H, NO, or NPh). The photophysics of these complexes was systematically investigated via spectroscopic methods and time-dependent density functional theory. All complexes possess strong ligand-localized π,π* transitions mixed with ligand-to-ligand charge transfer (LLCT)/metal-to-ligand charge transfer (MLCT) transitions below 400 nm, and a broad and featureless absorption band above 400 nm that arises from the N^N ligand-localized π,π*/ILCT (intraligand charge transfer) transitions as well as the very weak LLCT/MLCT transitions at longer wavelengths. The electron-withdrawing NO substituent on the N^N ligand leads to a blue-shift of the π,π*/ILCT absorption band, while the electron-donating NPh substituent causes a pronounced red-shift of this band. The unsubstituted and NO-substituted complexes (complexes 1 and 2, respectively) are moderately emissive at room temperature (RT) in solution as well as at 77 K in the glassy matrix, while the NPh-substituted complex (3) is weakly emissive at RT, but the emission becomes much brighter at 77 K. Complexes 1 and 2 show very broad and strong triplet excited-state absorption from 460 to 800 nm with moderately long lifetimes, while complex 3 exhibits weak but broad absorption bands from 384 to 800 nm with a longer lifetime than those of 1 and 2. The nonlinear transmission experiment manifests that complexes 1 and 2 are strong reverse saturable absorbers (RSA) at 532 nm, while 3 shows weaker RSA at this wavelength. These results clearly demonstrate that it is feasible to tune the ground-state and excited-state properties of the Ir(III) complexes via the terminal substituents at the diimine ligand. By introducing the fluoren-2-yl groups to the 2,2'-biquinoline ligand to extend the diimine ligand π-conjugation, we can obtain Ir(III) complexes with reasonably long-lived and strongly absorbing triplet excited state while red-shifting their LLCT/MLCT absorption band into the near-IR region. These features are critical in developing visible to near-IR broadband reverse saturable absorbers.
A series of monocationic iridium(III) complexes, [Ir(C^N) 2 (pqu)] + PF 6 − [pqu = 2-(pyridin-2-yl)quinoline, C^N = 2-phenylquinoline (1), 3-phenylisoquinoline (2), 1-phenylisoquinoline (3), benzo[h]quinoline (4), 2-(pyridin-2-yl)naphthalene (5), 1-(pyridin-2-yl)naphthalene ( 6), 2-(phenanthren-9-yl)pyridine ( 7), 2-phenylbenzo[g]quinoline (8), 2-(napht ha l e n -2 -y l )q u i n o l i n e ( 9 ) , a n d 2 -( n a p h t h a l e n -2yl)benzo[g]quinoline (10)], were synthesized in this work. These complexes bear C^N ligands with varied degrees of π conjugation and sites of benzannulation, allowing for elucidation of the effects of the benzannulation site at the C^N ligand on the photophysics of the complexes. Ultraviolet−visible (UV−vis) absorption and emission of the complexes were systematically investigated via spectroscopic techniques and time-dependent density functional theory calculations. Their triplet excited-state absorption and reverse saturable absorption (RSA) were studied by nanosecond transient absorption (TA) spectroscopy and nonlinear transmission techniques. The fusion of phenyl ring(s) to the phenyl ring or the 4 and 5 positions of the pyridyl ring of the C^N ligand resulted in red-shifted UV−vis absorption and emission spectra in complexes 2, 5−7, 9, and 10 compared to those of the parent complex 0, while their triplet lifetimes and emission quantum yields were significantly reduced. In contrast, the fusion of one phenyl ring to the other sites of the pyridyl group of the C^N ligand showed an insignificant impact on the energies of the lowest singlet (S 1 ) and triplet (T 1 ) excited states in complexes 1, 3, and 4 but noticeably affected their TA spectral features. The fusion of the naphthyl group to the 5 and 6 and positions at the pyridyl ring did not influence the S 1 energy of complex 8 but altered the nature of the T 1 states in 8 and 10 by switching them to the benzo[g]quinoline-localized 3 π,π* state, which resulted in completely different emission and TA spectra in these two complexes. The site-dependent variations of the ground-and excited-state absorption induced strong but varied RSA from these complexes for 4.1-ns laser pulses at 532 nm, with the RSA strength decreasing in the trend of 3 > 7 ≈ 4 ≈ 9 ≈ 6 > 8 ≈ 1 ≈ 2 ≈ 5 > 10.
Cadmium chalcogenide quantum dots (QDs) passivated by thiol-based ligands exhibit several advantages in their applications in lighting, sensing, and imaging technologies. However, their emission is sensitive to thiol concentrations, pH conditions, and temperatures. Using calculations based on the density functional theory, we identify conditions for thiol/thiolate equilibrium at the CdS QD surface that either eliminate or introduce optically inactive hole trap states favoring or disfavoring the emission. Our calculations indicate much weaker interactions between the QD and protonated species (thiols), compared to their deprotonated counterparts (thiolates). Additionally, the surface of CdS QD facilitates the partial deprotonation of thiols, leading to the formation of an additional stable networking conformation where the proton is shared between the ligand and the QD surface. Thiolates strongly reduce the optical intensity of low-energy transitions in CdS QDs, contributing thiolate-localized hole trap states at the QD band gap. However, networking between the thiols and the surface, as well as the presence of native ligands such as primary amines, stabilize such trap states brightening the lowest optical transitions. This explains the increased emission of thiol-passivated QDs at lower concentrations in neutral or acidic solutions. Surface-mediated bias toward deprotonated species and their contribution to optically inactive states also rationalizes irreversible emission quenching and bleaching in the CdSe/CdS QDs exposed to high temperatures or intensive laser pulse.
Exchanging the native surface ligands of CdSe nanocrystals with phenyldithiocarbamate molecules is known to red-shift the absorption spectrum and improve the conductivity of nanocrystal films. However, the mechanism of exchange and the details on the interaction between the nanocrystal surface and phenyldithiocarbamates have not been fully resolved. Using NMR and density functional theory calculations, we show that phenyldithiocarbamates decompose during exchange with native ligands. Phenyldithiocarbamate salts decompose when the cation (triethylammonium in this study) acts as an acid, donating a proton to the 3,5-dimethylphenyldithiocarbamate ligand (DMPTC) producing 3,5-dimethylaniline, carbon disulfide, and other decomposition products. While most decomposition products negligibly interact with the nanocrystal surface, 3,5-dimethylaniline chemically binds to the CdSe nanocrystals. This work demonstrates that the ligand exchange between colloidal nanocrystals and phenyldithiocarbamate ligands occurs in a dynamic system with a variety of molecular species.
Ten biscyclometalated monocationic Ir(III) complexes were synthesized and studied to elucidate the effects of extending π-conjugation of the diimine ligand (N^N = 2,2′-bipyridine in, and 1,1′-biisoquinoline in Ir10) via benzannulation at 2,2′-bipyridine on the excited-state properties and reverse saturable absorption (RSA) of these complexes. Either a bathochromic or a hypsochromic shift of the charge-transfer absorption band and emission spectrum was observed depending on the benzannulation site at the 2,2′-bipyridine ligand. Benzannulation at the 3,4-/3′,4′-position or 5,6-/5′,6′-position of 2,2′-bipyridine ligand or at the 6,7-position of the quinoline ring on the N^N ligand caused red-shifted charge-transfer absorption band and emission band for complexes Ir2, Ir8, Ir10 vs Ir1 and Ir3 vs Ir2, while benzannulation at the 4,5-/4′,5′-position of 2,2′-bipyridine ligand or at the 7,8-position of the quinoline ring on the N^N ligand induced a blue shift of the charge-transfer absorption and emission bands for complex Ir9 vs Ir1 and Ir4 vs Ir2. However, benzannulation at the 2,2′,3,3′-position of 2,2′-bipyridine or 5,6-position of phenanthroline ligand had no impact on the energy of the chargetransfer absorption band and emission band of complexes Ir5−Ir7 compared with those of Ir1. The observed phenomenon was explained by the frontier molecular orbital (FMO) symmetry analysis. Site-dependent benzannulation also impacted the spectral feature and intensity of the triplet transient absorption spectra and lifetimes drastically. Consequently, the RSA strength of these complexes varied with a trend of Ir7 > Ir5 ≈ Ir6 ≈ Ir1 > Ir3 > Ir2 > Ir10 > Ir4 > Ir8 > Ir9 at 532 nm for 4.1 ns laser pulses.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.