Lifetime Of Triplet Excited State Research Articles

Structure-Activity Relationship of Benzophenazine Derivatives for Homogeneous and Heterogenized Photooxygenation Catalysis.

Singlet oxygen is a powerful oxidant used in various applications, such as organic synthesis, medicine, and environmental remediation. Organic and inorganic photosensitizers are commonly used to generate this reactive species through energy transfer with the triplet ground state of oxygen. We describe here a series of novel benzophenazine derivatives as a promising class of photosensitizers for singlet oxygen photosensitization. In this study, we investigated the structure-activity relationship of these benzophenazine derivatives. Akin to a molecular compass, the southern fragment was first functionalized with either aromatic tertiary amines, alkyl tertiary amines, aromatic sulfur groups, alkyl sulfur groups, or cyclic ethers. Enhanced photophysical properties (in terms of triplet excited-state lifetime, absorption wavelength, triplet state energy, and O2 quenching capabilities) were obtained with cyclic ether and sulfur groups. Conversely, the presence of an amine moiety was detrimental to the photocatalysts. The western and northern fragments were also investigated and slightly undesirable to negligible changes in photophysical properties were observed. The most promising candidate was then immobilized on silica nanoparticles and its photoactivity was evaluated in the citronellol photooxidation reaction. A high NMR yield of 97 % in desired product was obtained, with only a slight decrease over several recycling runs (85 % in the fourth run). These results provide insights into the design of efficient photosensitizers for singlet oxygen generation and the development of heterogeneous systems.

Luminescent Platinum(II) Complexes with Stimuli-Responsive Flexible Lewis Pair Ligands: Spectroscopic and Computational Studies.

A series of new luminescent bimetallic platinum(II) complexes with stimuli-responsive flexible Lewis pair (FlexLP) ligands are described. The FlexLP ligands consist of a dimesitylboron Lewis acid and diphenylphosphine oxide Lewis base which are in equilibrium between the unbound open form and the Lewis adduct, controlled by the hydrogen bond donating strength of the solvent. Spectroscopic techniques and density functional theory (DFT) calculations were used to interpret the photophysics of the platinum(II) complexes. All complexes exhibit tunable absorption in the region of 300-500 nm and green to orange photoluminescence, depending on the ratio of weak (THF) to strong (MeOH) hydrogen bond donating solvent employed. Spectroscopic and computational data shows that phosphine and peripheral acetylide ligands on the platinum(II) centers have limited influence on the emission energy, indicating the emission originates from the FlexLP-dominated fluorescence. Using time-resolved transient absorption spectroscopy it is shown that the complexes undergo intersystem crossing (ISC) to the triplet-excited state upon photoexcitation, and the ISC efficiency is affected by the peripheral acetylide ligands. The triplet-excited state lifetime can also be manipulated by the state of the FlexLP ligand, with the closed form complexes having longer lifetimes than the open form complexes.

Management of Triplet States in Modified Mononuclear Ruthenium(II) Complexes for Enhanced Photocatalysis.

Controlling the interplay between relaxation and charge/energy transfer processes in the excited states of photocatalysts is crucial for the performance of artificial photosynthesis. Metal-to-ligand charge-transfer triplet states (3MLCT*) of ruthenium(II) complexes are broadly implemented for photocatalysis, but an effective means of managing the triplets for enhanced photocatalysis has been lacking. Herein, We proposed a strategy to considerably prolong the triplet excited-state lifetime by decorating a ruthenium(II) phosphine complex (RuP-1) with pendent polyaromatic hydrocarbons (PAHs). Systematic studies demonstrate that in RuP-4 decorated with anthracene, sub-picosecond electron transfer from anthracene to 3MLCT* leads to a charge-separated state that can mediate the formation of the intra-ligand triplet state (3IL) of anthracene, resulting in an exceptionally long excited-state up to several milliseconds. This triplet management strategy enables impressive photocatalytic reduction of CO2 to CO with a turnover number (TON) of 404, an optimized quantum yield of 43 % and 100 % selectivity, which is the highest reported performance for mononuclear photocatalysts without additional photosensitizers. RuP-4 also catalyzes photochemical hydrogen generation under argon. This work opens up an avenue for regulating the excited-state charge/energy flow for the development of long-lived 3IL multi-functional mononuclear photocatalysts to boost artificial photosynthesis.

Novel Photocatalyst Based on Through‐Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low‐Power Excitation Light

AbstractCurrently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (<50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm.

A 700nm LED light activated Ru(II) complex destroys tumor cytoskeleton via photosensitization and photocatalysis.

Photoactivable chemotherapy (PACT) using metallic complexes provides spatiotemporal selectivity over drug activation for targeted anticancer therapy. However, the poor absorption in near-infrared (NIR) light region of most metallic complexes renders tissue penetration challenging. Herein, we present an NIR light triggered di-nuclear photoactivable Ru(II) complex (Ru2) and comprehensively investigated the antitumor mechanism. The introduction of a donor-acceptor-donor (D-A-D) linker greatly enhances the intramolecular charge transition, resulting in a high molar extinction coefficient in the NIR region with an extended triplet excited state lifetime. Most importantly, when activated by 700nm NIR light, Ru2 exhibits unique slow photodissociation kinetics that facilitates synergistic photosensitization and photocatalytic activity to destroy diverse intracellular biomolecules. In vitro and in vivo experiments show that when activated by 700nm NIR light, Ru2 exhibits nanomolar photocytotoxicity toward 4T1 cancer cells via the induction of calcium overload and endoplasmic reticulum (ER) stress. These findings provide a robust foundation for the development of NIR-activated Ru(II) PACT complexes for phototherapeutic application. This article is protected by copyright. All rights reserved.

Modulation of lanthanide luminescence by carbamoylmethylphosphine oxide ligand: A theoretical study

The antenna capacity of Phenacyldiphenylphosphine oxide (Phenac), combining C=O and P=O donor groups was established by theoretical examination of its chromophore properties, binding ability to encapsulate and stabilize lanthanide complexes and potential to sensitize the EuIII and TbIII luminescence in Eu(Phenac)2(NO3)3(H2O) (1), Eu(Phenac)2(NO3)3 (2), Eu(Phenac)3(NO3)3 (3) and Tb(Phenac)2(NO3)3(H2O) (4) complexes in vacuum, solution and solid phase. The ligand-centered singlet and triplet excited state energies, the rates and lifetimes for the rival nonradiative (S1→T1,2 intersystem crossing (ISC)) and radiative and nonradiative S1→S0 and T1→S0 relaxation were predicted by means of DFT/TDDFT/ωB97XD calculations. Similar relaxation paths were found for all complexes. The absorbed energy by Sn > 1(π-π*) states relaxed to T1min by major ISC mechanism S1→T2→T1. The long radiative lifetime of S1→S0 due to n(p(C)(O))π-π*,p(P) character facilitated the forward ISC process. The environment, Phenac's number and LnIII size affect the T1 energy ∼0.1 eV. The calculated (Phenac→EuIII) energy transfer rates suggested the most likely T1 → 5D1/5D0 channels for a population of emitting metal-centered states. The small Φ of EuIII and larger luminescence of TbIII were discussed and explained. The importance of the P=O and C=O groups for the coordination ability and absorption properties of Phenac has been elucidated.

Comprehensive Photophysical and Nonlinear Spectroscopic Study of Thioanisolyl‐Picolinate Triazacyclononane Lanthanide Complexes

AbstractDetailed photophysical studies of luminescent lanthanide complexes are presented and elaborated using a newly developed thioanisolyl‐picolinate antenna and the related tacn macrocyclic ligand. The new ligand proved to sensitise Nd(III), Sm(III), Eu(III) and Yb(III) emission. Eu(III) complex showed complete energy transfer, yielding high quantum yield (44 %) and brightness, while the Tb(III) analogue underwent a thermally activated back‐energy transfer, resulting in a strong oxygen quenching of the triplet excited state. Transient absorption spectroscopy measurements of Gd(III), Tb(III) and Eu(III) compounds confirmed the sensitization processes upon the charge‐transfer antenna excitation. The triplet excited state lifetime of the Tb(III) complex was 5‐times longer than that of the Gd(III) analogue. In contrast, the triplet state was totally quenched by the energy transfer to the 4f‐metal ion in the Eu(III) species. Nonlinear two‐photon absorption highlighted efficient biphotonic sensitization in Eu(III) and Sm(III) complexes. In case of the Nd(III) compound, one‐photon absorption in 4f–4f transitions was predominant, despite the excitation at the antenna two‐photon band. This phenomenon was due to the Nd(III) 4f–4f transitions overlapping with the wavelength‐doubled absorption of the complex.

Sb(V) dihalide corroles: efficient singlet oxygen photosensitisers.

Sb(V) dihalide corrole complexes, in particular difluoro-5,15-di(4-cyanophenyl)-10-(2,4,5-trimethoxyphenyl)corrolatoantimony(V) (complex 1), show distinct emission properties and efficient intersystem crossing rates. Furthermore, complex 1 is characterised by its extended triplet excited state lifetime and an impressive singlet oxygen quantum yield exceeding 95%. This emphasises its potential for effective photooxidation reactions, positioning it as a leader in Sb(V) complex applications.

Impact of Alkyl Core Substitution Kinetics in Diaryl Dihydrophenazine Photoredox Catalysts on Properties and Performance in O-ATRP.

Organocatalyzed atom transfer radical polymerization (O-ATRP) is a controlled radical polymerization method mediated by organic photoredox catalysts (PCs) for producing polymers with well-defined structures. While N,N-diaryl dihydrophenazine PCs have successfully produced polymers with low dispersity (Đ < 1.3) in O-ATRP, low initiator efficiencies (I* ~ 60-80%) indicate an inability to achieve targeted molecular weights and have been attributed to the addition of radicals to the PC core. In this work, we measure the rates of alkyl core substitution (AkCS) to gain insight into why PCs differing in N-aryl group connectivity exhibit differences in polymerization control. Additionally, we evaluate how PC properties evolve during O-ATRP when a non-core-substituted PC is used. PC 1 with 1-naphthyl groups in the N-aryl position resulted in faster AkCS (k 1 = 1.21 ± 0.16 × 10-3 s-1, k 2 = 2.04 ± 0.11 × 10-3 s-1) and better polymerization control at early reaction times as indicated by plots of molecular weight (number average molecular weight = M n) vs conversion compared to PC 2 with 2-naphthyl groups (k 1 = 6.28 ± 0.38 × 10-4 s-1, k 2 = 1.15 ± 0.07 × 10-3 s-1). The differences in rates indicate that N-aryl connectivity can influence polymerization control by changing the rate of AkCS PC formation. The rate of AkCS increased from the initial to the second substitution, suggesting that PC properties are modified by AkCS. Increased PC radical cation (PC•+) oxidation potentials (E 1/2 = 0.26-0.27 V vs SCE) or longer triplet excited-state lifetimes (τ T1 = 1.4-33 μs) for AkCS PCs 1b and 2b compared to parent PCs 1 and 2 (E 1/2 = 0.21-0.22 V vs SCE, τ T1 = 0.61-3.3 μs) were observed and may explain changes to PC performance with AkCS. Insight from evaluation of the formation, properties, and performance of AkCS PCs will facilitate their use in O-ATRP and in other PC-driven organic transformations.

The interplay of vibronic and spin-orbit coupling in the fluorescence quenching in trans-dithionated PDI.

Organic chromophores such as the thionated derivatives of perylene diimides (PDIs) show prolonged triplet-excited state lifetimes in contrast to their pristine parent PDI molecule, which shows near unity fluorescence quantum yield. The excited state dynamics in the trans-dithionated PDI (S2-PDI) are studied here. Unlike PDI, the photo absorbing ππ* state of S2-PDI is in close proximity to quasi-degenerate nπ* states. The latter exhibits an interesting vibronic problem leading to the breaking of orbital symmetry mediated through non-totally symmetric vibrations. The time-dependent quantum dynamics are studied with a diabatic model Hamiltonian involving three singlet and three triplet states coupled via 22 vibrational modes. A combined effect of multiple internal-conversion and inter-system crossing (ISC) pathways leads to population transfer from the 1ππ* state to the 3ππ* state via the nπ* states, with an overall ISC rate of 0.70ps that compares well with the experimental value. The calculated absorption spectra for PDI and S2-PDI reproduce the essential vibronic features in the observed experimental spectra. The dominant vibronic progressions are found to have significant contributions from the vinyl stretching modes of the PDI core.

Long‐lived Triplet Excited State of Perylenemonoimide (PMI) in a Diimine Pt(II) Bis‐acetylide Complex: Preparation and Study of the Photophysical Property with Transient Spectra

AbstractWe prepared a N^N Pt(II) bisacetylide complex that has strong absorption of visible light (molar absorption coefficients ϵ=6.7×104 M−1 cm−1 at 570 nm), and the singlet oxygen quantum yield (ΦΔ) is up to 78 %. Femtosecond transient absorption spectra show the intersystem crossing (ISC) of the complex takes 81.8 ps, nanosecond transient absorption spectra show the triplet excited state lifetime is 7.6 μs. Density functional theory (DFT) computation demonstrated that the S1 and T1 states are mainly localized on the perylenemonoimide (PMI) ligands, although the involvement of the Pt(II) centre is noticeable. The complex was used as triplet photosensitizer to generate delayed fluorescence with perylenebisimide (PBI) as the triplet state energy acceptor and emitter, via the intermolecular triplet‐triplet energy transfer (TTET) and triplet‐triplet annihilation (TTA), the delayed fluorescence lifetime is up to 52.5 μs under the experimental conditions.

Two-Step Synthesis of B2 N2 -Doped Polycyclic Aromatic Hydrocarbon Containing Pentagonal and Heptagonal Rings with Long-Lived Delayed Fluorescence.

Pentagon-heptagon embedded polycyclic aromatic hydrocarbons (PAHs) have aroused increasing attention in recent years due to their unique physicochemical properties. Here, for the first time, this report demonstrates a facile method for the synthesis of a novel B2 N2 -doped PAH (BN-2) containing two pairs of pentagonal and heptagonal rings in only two steps. In the solid state of BN-2, two different conformations, including saddle-shaped and up-down geometries, are observed. Through a combined spectroscopic and calculation study, the excited-state dynamics of BN-2 is well-investigated in this current work. The resultant pentagon-heptagon embedded B2 N2 -doped BN-2 displays both prompt fluorescence and long-lived delayed fluorescence components at room temperature, with the triplet excited-state lifetime in the microsecond time region (τ= 19 µs). The triplet-triplet annihilation is assigned as the mechanism for the observed long-lived delayed fluorescence. Computational analyses attributed this observation to the small energy separation between the singlet and triplet excited states, facilitating the intersystem crossing (ISC) process which is further validated by the ultrafast spectroscopic measurements.

Photophysical properties of Pt(II) and Pd(II) complexes for two-photon photodynamic therapy: A computational investigation

Two-photon photodynamic therapy (TP-PDT) plays a critical role of in cancer treatment due to its deep penetration into tissue and low photobleaching effect. In this paper, density functional theory (DFT) and time-dependent density functional theory (TDDFT) are used to calculate the one and two-photon absorption properties, spin-orbit coupling constants, triplet excited state lifetimes and type I/II mechanisms of Pt(II) complexes and two designed Pd(II) complexes. The results reveal that all complexes meet the standard of photosensitizer. More importantly, the designed Pd(II) complex 3 possesses both large two-photon absorption cross section up to 134.5 GM and long triplet excited state lifetime of 85.5 μs. It is expected that the inexpensive Pd(II) complex will replace the reported Pt(II) complexes as an effective two-photon absorption photosensitizer, which will provide some guidance for the design and synthesis of novel photosensitizers experimentally.

Benchmarking DFT functionals for photophysics of pyranoflavylium cations

An intense absorption, phosphorescence, a long triplet excited state lifetime and singlet oxygen generation capabilities are characteristics of pyranoflavylium cations, analogues to pyranoanthocyanidins originated in the maturation process of red wine. Such properties make these compounds potential photosensitizers to be applied in photodynamic therapy. In this context, the photophysical processes underlying that treatment critically depend on the electronic structure of the pyranoflavylium molecules. When employing density functional theory to describe the electronic structure of molecules, the choice of the most suitable functional is not trivial, and benchmark studies are needed to orient practitioners in the field. In this work, a benchmark of seven of the most commonly used density functionals in addressing the photophysical properties of a set of eight pyranoflavylium cations is reported. Ground and excited state geometries, molecular orbitals, and absorption, fluorescence and phosphorescence transition energies were calculated using density functional theory approaches, and evaluated and compared to experimental data and monoreferential wave function-based methodologies. Statistical analysis of the results indicates that global-hybrid functionals allow an excellent description of absorption and emission energies, with errors around 0.05 eV, while range-separated variants led to somewhat larger errors in the range 0.1–0.2 eV. In contrast, range-separated functionals display excellent phosphorescence energies with errors close to 0.05 eV, in this case global-hybrids showing increased discrepancies around 0.5–0.1 eV.

Photophysical Exploration of Zn(II) Polypyridine Photosensitizers in Two-Photon Photodynamic Therapy: Insights from Theory.

The high incidence and difficulties of treatment of cancer have always been a challenge for mankind. Two-photon photodynamic therapy (TP-PDT) as a less invasive technique provides a new perspective for tumor treatment due to its low-energy near-infrared excitation, high targeting, and minor damage. At present, the emerging metal complexes used as the photosensitizers (PSs) in TP-PDT have aroused great interest. However, most metal complexes as PSs in TP-PDT still face some problems, such as slow clearance, unsatisfactory two-photon absorption (TPA) characteristics, high price, low reactivity, and poor solubility. In this work, density functional theory and time-dependent density functional theory were used to characterize the one/two-photon response, solvation free energy, and lipophilicity of a series of novel PSs applied in TP-PDT. The results suggest that based on complex 1, replacing Ru(II) center with Zn(II) (complex 2) can effectively prolong the triplet excited state lifetime while reducing the cost and environmental pollution, and the azetidine heterospirocycles were introduced into the ligand scaffold (complex 3), which effectively reduced the vibration relaxation of the ligand group and improved the water solubility; further, the addition of acetylenyl groups subtly enhanced the light absorption and significantly improved the two-photon response (complex 4). In addition, all complexes met the requirement of a PS and could be used as potential candidates for TP-PDT. In particular, complex 4 has the advantages of high solvation free energy, a large TPA cross-section (1413 GM), a long triplet state lifetime (671 μs), good chemical reactivity, and low cost, and it is easy to be scavenged by organisms. Overall, this contribution may provide an important clue to formulate clear design principles for type I/II PSs and rational design of PSs with high intersystem crossing rates, a long lifetime, and therapeutic excitation wavelengths.

Avoiding One-Electron Oxidation of Biomolecules by 3,4-Dihydroxy-L-Phenylalanine (DOPA)†.

It has been proposed that 3,4-dihydroxy-L-phenylalanine (DOPA) has antioxidant properties, and thus, the objective of this work was to evaluate the effect of adding DOPA during the photosensitized oxidation of tyrosine (Tyr), tryptophan (Trp), histidine (His), 2'-deoxyguanosine 5'-monophosphate (dGMP) and 2'-deoxyadenosine 5'-monophosphate (dAMP). It was observed that, upon pterin-photosensitized degradation of a given biomolecule in acidic aqueous solutions, the rate of the biomolecule consumption decreases due to the presence of DOPA. Although DOPA deactivates the excited states of pterin (Ptr), biomolecules do as well, being the bimolecular quenching constants in the diffusional control limit, indicating that DOPA antioxidant mechanism is not a simple deactivation of Ptr excited states. Laser flash photolysis experiments provide evidence of the formation of DOPA radical (DOPA(-H)• , λMAX 310 nm), which is formed in a timescale longer than Ptr triplet excited state (3 Ptr*) lifetime, ruling out its formation in a reaction between DOPA and 3 Ptr*. The experimental results presented in this work indicate that the observed decrease on the rate of each biomolecule consumption due to the presence of DOPA is through a second one-electron transfer reaction from DOPA to the biomolecule radicals.

Revealing excited-state dynamics of type I zinc phthalocyanine photosensitizer for photodynamic therapy

<p indent="0mm">Photodynamic therapy is a clinically approved novel therapeutic technique that employs photosensitizer in the presence of suitable light to produce a cytotoxic reactive oxygen species (ROS). According to the ROS types, photosensitizers are divided into Type I (free radical) and Type II (singlet oxygen). Compared with Type II, Type I has low dependence on oxygen, presenting excellent prospects in overcoming the limitations of the hypoxic cancer treatment. However, there is a limited scope of Type I photosensitizers. Moreover, few studies concentrated on the mechanism research, which hinders the development of Type I photodynamic therapy. This study proved that zinc phthalocyanate (ZnPc) has a negligible singlet-triplet energy gap, ultrafast intersystem crossing rate (3.8× <sc>10⁶ s⁻¹),</sc> and a long triplet excited state lifetime <sc>(327 ns),</sc> all of these together give rise to facile triplet-photosensitization. Furthermore, ZnPc exhibits efficient generation of superoxide anion radicals and hydroxyl radicals but negligible singlet oxygen production, validating its Type I feature. Finally, we demonstrated the preliminary <italic>in vitro</italic> photodynamic therapy mediated by ZnPc.

Best practice in determining key photophysical parameters in triplet–triplet annihilation photon upconversion

Triplet–triplet annihilation photon upconversion (TTA-UC) is a process in which low-energy light is transformed into light of higher energy. During the last two decades, it has gained increasing attention due to its potential in, e.g., biological applications and solar energy conversion. The highest efficiencies for TTA-UC systems have been achieved in liquid solution, owing to that several of the intermediate steps require close contact between the interacting species, something that is more easily achieved in diffusion-controlled environments. There is a good understanding of the kinetics dictating the performance in liquid TTA-UC systems, but so far, the community lacks cohesiveness in terms of how several important parameters are best determined experimentally. In this perspective, we discuss and present a “best practice” for the determination of several critical parameters in TTA-UC, namely triplet excited state energies, rate constants for triplet–triplet annihilation (k_{{{text{TTA}}}}), triplet excited-state lifetimes (tau_{{text{T}}}), and excitation threshold intensity (I_{{{text{th}}}}). Finally, we introduce a newly developed method by which k_{{{text{TTA}}}}, tau_{{text{T}}}, and I_{{{text{th}}}} may be determined simultaneously using the same set of time-resolved emission measurements. The experiment can be performed with a simple experimental setup, be ran under mild excitation conditions, and entirely circumvents the need for more challenging nanosecond transient absorption measurements, a technique that previously has been required to extract k_{{{text{TTA}}}}. Our hope is that the discussions and methodologies presented herein will aid the photon upconversion community in performing more efficient and manageable experiments while maintaining—and sometimes increasing—the accuracy and validity of the extracted parameters.

Viscosity Effects on Excited-State Dynamics of Indocyanine Green for Phototheranostic.

The excited-state dynamics of indocyanine green (ICG) fundamentally determine its photophysical properties for phototheranostic. However, its dynamics are predictable to be susceptible toward intracellular viscosity due to its almost freely rotating structure, making the precise phototheranostic very challenging. Therefore, correlating the viscosity with the dynamics of ICG is of great importance and urgency for precise phototheranostic prospects. This study presents systemic investigations on the viscosity-dependent dynamics of ICG for phototheranostic. Femtosecond transient absorption (fs-TA) experiments elucidate a prolonged radiative transition (225 ps vs 152 ps) for ICG in a viscous environment, which benefits fluorescence. High viscosity remarkably extends the triplet excited-state lifetime of ICG but reduces its internal conversion (6.2 ps vs 2.2 ps). The extended triplet lifetime affords sufficient photosensitization time to enhance photodynamic therapy. A moderative internal conversion is unfavorable for heat production, resulting in inferior photothermal therapy. With this clear picture of excitation energy state dissipation in mind, we readily identified the safety laser power density for precise phototheranostic. This work provides an insightful understanding of viscosity-relevant excited-state dynamics toward phototheranostic, which is also beneficial for designing novel ICG derivatives with improved phototheranostic performance.

Singlet Oxygen Generation in Peripherally Modified Platinum and Palladium Porphyrins: Effect of Triplet Excited State Lifetimes and meso-Substituents on 1 O2 Quantum Yields.

A series of meso-substituted with aromatic (=tolyl, pyrenyl, fluorenyl, naphthyl, and triphenylamine) substituents, platinum (Pt), and palladium (Pd) porphyrins have been synthesized and characterized by spectroscopic and single-crystal X-ray diffraction studies to probe structure-reactivity aspects on the electrochemical redox potentials, and phosphorescence quantum yields and lifetimes. In the X-ray structures, the aromatic meso-substituents were rotated to some extent from the planarity of the porphyrin ring to minimize steric hindrance. Both Pt and Pd porphyrins revealed higher electrochemical redox gaps as compared to their free-base porphyrin analogs as a result of the harder oxidation and reduction processes. The ability of both Pt and Pd porphyrins to generate singlet oxygen was probed by monitoring the photoluminescence of 1 O2 at 1270 nm. Higher quantum yields for both triplet sensitizers compared to their free-base analogs were witnessed. Singlet oxygen quantum yields close to unity were possible to achieve in the case of Pt and Pd porphyrins bearing triphenylamine substituents at the meso-position. The present study brings out the importance of different meso-substituents on the triplet porphyrin sensitizers in governing singlet oxygen quantum yields; a key property of photosensitizers needed for photodynamic therapy, chemical synthesis, and other pertinent applications.