skip to main content

This content will become publicly available on December 1, 2023

Title: Two-photon-absorbing ruthenium complexes enable near infrared light-driven photocatalysis
Abstract One-photon-absorbing photosensitizers are commonly used in homogeneous photocatalysis which require the absorption of ultraviolet (UV) /visible light to populate the desired excited states with adequate energy and lifetime. Nevertheless, the limited penetration depth and competing absorption by organic substrates of UV/visible light calls upon exploring the utilization of longer-wavelength irradiation, such as near-infrared light (λ irr  > 700 nm). Despite being found applications in photodynamic therapy and bioimaging, two-photon absorption (TPA), the simultaneous absorption of two photons by one molecule, has been rarely explored in homogeneous photocatalysis. Herein, we report a group of ruthenium polypyridyl complexes possessing TPA capability that can drive a variety of organic transformations upon irradiation with 740 nm light. We demonstrate that these TPA ruthenium complexes can operate in an analogous manner as one-photon-absorbing photosensitizers for both energy-transfer and photoredox reactions, as well as function in concert with a transition metal co-catalyst for metallaphotoredox C–C coupling reactions.
Authors:
; ; ; ; ;
Award ID(s):
2102508 1955358
Publication Date:
NSF-PAR ID:
10332335
Journal Name:
Nature Communications
Volume:
13
Issue:
1
ISSN:
2041-1723
Sponsoring Org:
National Science Foundation
More Like this
  1. This minireview focuses on recent progress in developing heavy-atom-free photosensitizers based on the thionation of nucleic acid derivatives and other biocompatible organic compounds for prospective applications in photodynamic therapy. Particular attention is given to the use of thionated nucleobase derivatives as “ one-two punch ” photodynamic agents. These versatile photosensitizers can act as “ Trojan horses ” upon metabolization into DNA and exposure to activating light. Their incorporation into cellular DNA increases their selectivity and photodynamic efficacy against highly proliferating skin cancer tumor cells, while simultaneously enabling the use of low irradiation doses both in the presence and in themore »absence of molecular oxygen. Also reviewed are their primary photochemical reactions, modes of action, and photosensitization mechanisms. New developments of emerging thionated organic photosensitizers absorbing visible and near-infrared radiation are highlighted. Future research directions, as well as, other prospective applications of heavy-atom-free, thionated photosensitizers are discussed.« less
  2. A series of five ruthenium complexes containing triphenyl phosphine groups known to enhance both cellular penetration and photoinduced ligand exchange, cis -[Ru(bpy) 2 (P( p -R-Ph) 3 )(CH 3 CN)] 2+ , where bpy = 2,2′-bipyridine and P( p -R-Ph) 3 represent para -substituted triphenylphosphine ligands with R = –OCH 3 (1), –CH 3 (2) –H (3), –F (4), and –CF 3 (5), were synthesized and characterized. The photolysis of 1–5 in water with visible light ( λ irr ≥ 395 nm) results in the substitution of the coordinated acetonitrile with a solvent molecule, generating the corresponding aqua complex asmore »the single photoproduct. A 3-fold variation in quantum yield was measured with 400 nm irradiation, Φ 400 , where 1 is the most efficient with a Φ 400 = 0.076(2), and 5 the least photoactive complex, with Φ 400 = 0.026(2). This trend is unexpected based on the red-shifted metal-to-ligand charge transfer (MLCT) absorption of 1 as compared to that of 5, but can be correlated to the substituent Hammett para parameters and p K a values of the ancillary phosphine ligands. Complexes 1–5 are not toxic towards the triple negative breast cancer cell line MDA-MB-231 in the dark, but 3 and 5 are >4.2 and >19-fold more cytotoxic upon irradiation with blue light, respectively. A number of experiments point to apoptosis, and not to necrosis or necroptosis, as the mechanism of cell death by 5 upon irradiation. These findings provide a foundation for understanding the role of phosphine ligands on photoinduced ligand substitution and show the enhancement afforded by –CF 3 groups on photochemotherapy, which will aid the future design of photocages for photochemotherapeutic drug delivery.« less
  3. Two new tris-heteroleptic Ru( ii ) complexes with triphenylphosphine (PPh 3 ) coordination, cis -[Ru(phen) 2 (PPh 3 )(CH 3 CN)] 2+ (1a, phen = 1,10-phenanthroline) and cis -[Ru(biq)(phen)(PPh 3 )(CH 3 CN)] 2+ (2a, biq = 2,2′-biquinoline), were synthesized and characterized for photochemotherapeutic applications. Upon absorption of visible light, 1a exchanges a CH 3 CN ligand for a solvent water molecule. Surprisingly, the steady-state irradiation of 2a followed by electronic absorption and NMR spectroscopies reveals the photosubstitution of the PPh 3 ligand. Phosphine photoinduced ligand exchange with visible light from a Ru( ii ) polypyridyl complex has not previouslymore »been reported, and calculations reveal that it results from a trans -type influence in the excited state. Complexes 1a and 2a are not toxic against the triple negative breast cancer cell line MDA-MB-231 in the dark, but upon irradiation with blue light, the activity of both complexes increases by factors of >4.2 and 5.8, respectively. Experiments with PPh 3 alone show that the phototoxicity observed for 2a does not arise from the released phosphine ligand, indicating the role of the photochemically generated ruthenium aqua complex on the biological activity. These complexes represent a new design motif for the selective release of PPh 3 and CH 3 CN for use in photochemotherapy.« less
  4. The photothermal experiments on the incident light angle dependence are carried out using simulated solar light on thin films of both iron oxides (Fe3O4 and Fe3O4@Cu2-xS) and porphyrin compounds (chlorophyll and chlorophyllin). Fe3O4 and Fe3O4@Cu2-xS are synthesized using various solution methods that produce mono-dispersed nanoparticles on the order of 10 nm. Chlorophyll is extracted from fresh spinach and chlorophyllin sodium copper is a commercial product. These photothermal (PT) materials are dispersed in polymethyl methacrylate (PMMA) solutions and deposited on glass substrates via spin coating that result in clear and transparent thin films. The iron-oxide based thin films show distinctive absorptionmore »spectra; Fe3O4 exhibits a strong peak near UV and gradually decreases into the visible and NIR regions; the absorption of Fe3O4@Cu2-xS is similar in the UV region but shows a broad absorption in the NIR region. Both chlorophyll and chlorophyllin are characterized with absorption peaks near UV and NIR showing a “U”-shaped spectrum, ideally required for efficient solar harvest and high transparency in energy-efficient single-pane window applications. Upon coating of the transparent PT films on the window inner surfaces, solar irradiation induces the photothermal effect, consequently raising the film temperature. In this fashion, the thermal loss through the window can be significantly lowered by reducing the temperature difference between the window inner surface and the room interior, based on a new concept of so-called “optical thermal insulation” (OTI) without any intervention medium, such as air/argon, as required in the glazing technologies. Single-panes are therefore possible to replace double- or triple panes. As OTI is inevitably affected by seasonal and daily sunlight changes, an incident light angle dependence of the photothermal effect is crucial in both thin film and window designs. It is found that the heating curves reach their maxima at small angles of incidence while the photothermal effect is considerably reduced at large angles. This angle dependence is well explained by light reflection by the thin film surface, however, deviated from what is predicted by the Fresnel’s law, attributable to non-ideal surfaces of the substrates. The angle dependence data provides an important reference for OTI that window exposure to sun is greater at winter solstice while that is considerably reduced in the summer. This conclusion indicates much enhanced solar harvesting and heat conversion via optically insulated windows in the winter season, resulting in much lower U-factors.« less
  5. Abstract. To better understand the effects of wildfires on air quality andclimate, it is important to assess the occurrence of chromophoric compoundsin smoke and characterize their optical properties. This study explores themolecular composition of light-absorbing organic aerosol, or brown carbon(BrC), sampled at the Missoula Fire Sciences laboratory as a part of theFIREX Fall 2016 lab intensive. A total of 12 biomass fuels from different planttypes were tested, including gymnosperm (coniferous) and angiosperm(flowering) plants and different ecosystem components such as duff, litter,and canopy. Emitted biomass burning organic aerosol (BBOA) particles werecollected onto Teflon filters and analyzed offline using high-performanceliquid chromatography coupled tomore »a photodiode array spectrophotometer and a high-resolution mass spectrometer(HPLC–PDA–HRMS). Separated BrC chromophores were classified by theirretention times, absorption spectra, integrated absorbance in the near-UVand visible spectral range (300–700 nm), and chemical formulas from theaccurate m∕z measurements. BrC chromophores were grouped into the followingclasses and subclasses: lignin-derived products, which include lignin pyrolysisproducts; distillation products, which include coumarins and flavonoids;nitroaromatics; and polycyclic aromatic hydrocarbons (PAHs). The observedclasses and subclasses were common across most fuel types, although specific BrCchromophores varied based on plant type (gymnosperm or angiosperm) andecosystem component(s) burned. To study the stability of the observed BrCcompounds with respect to photodegradation, BBOA particle samples wereirradiated directly on filters with near UV (300–400 nm) radiation, followedby extraction and HPLC–PDA–HRMS analysis. Lifetimes of individual BrCchromophores depended on the fuel type and the corresponding combustioncondition. Lignin-derived and flavonoid classes of BrC generally hadthe longest lifetimes with respect to UV photodegradation. Moreover,lifetimes for the same type of BrC chromophores varied depending on biomassfuel and combustion conditions. While individual BrC chromophoresdisappeared on a timescale of several days, the overall light absorption bythe sample persisted longer, presumably because the condensed-phasephotochemical processes converted one set of chromophores into anotherwithout complete photobleaching or from undetected BrC chromophores thatphotobleached more slowly. To model the effect of BrC on climate, it isimportant to understand the change in the overall absorption coefficientwith time. We measured the equivalent atmospheric lifetimes of the overallBrC absorption coefficient, which ranged from 10 to 41 d, with subalpinefir having the shortest lifetime and conifer canopies, i.e., juniper, havingthe longest lifetime. BrC emitted from biomass fuel loads encompassingmultiple ecosystem components (litter, shrub, canopy) had absorptionlifetimes on the lower end of the range. These results indicate thatphotobleaching of BBOA by condensed-phase photochemistry isrelatively slow. Competing chemical aging mechanisms, such as heterogeneousoxidation by OH, may be more important for controlling the rate of BrCphotobleaching in BBOA.« less