Molecular Design of Highly Efficient Heavy-Atom-Free Triplet BODIPY Derivatives for Photodynamic Therapy and Bioimaging

Novel BODIPY photosensitizers were developed for imaging-guided photodynamic therapy. The introduction of a strong electron donor to the BODIPY core through a phenyl linker combined with the twisted arrangement between the donor and the BODIPY acceptor is essential for reducing the energy gap between the lowest singlet excited state and the lowest triplet state (ΔE_ST), leading to a significant enhancement in the intersystem crossing (ISC) of the BODIPYs. Remarkably, the BDP-5 with the smallest ΔE_ST (ca. 0.44 eV) exhibited excellent singlet oxygen generation capabilities in both organic and aqueous solutions. BDP-5 also displayed bright emission in the far-red/near-infrared region in the condensed states. More importantly, both in vitro and in vivo studies demonstrated that BDP-5 NPs displayed a high potential for photodynamic cancer therapy and bioimaging.     

Photoinduced Electron Transfer‐based Halogen‐free Photosensitizers: Covalent meso‐Aryl (Phenyl,Naphthyl, Anthryl,and Pyrenyl) as Electron Donors to Effectively Induce the Formation of the Excited Triplet State and Singlet Oxygen for BODIPY Compounds

Pristine BODIPY compounds have negligible efficiency to generate the excited triplet state and singlet oxygen. In this report, we show that attaching a good electron donor to the BODIPY core can lead to singlet oxygen formation with up to 58 % quantum efficiency. For this purpose, BODIPYs with meso ‐aryl groups (phenyl, naphthyl, anthryl, and pyrenyl) were synthesized and characterized. The fluorescence, excited triplet state, and singlet oxygen formation properties for these compounds were measured in various solvents by UV/Vis absorption, steady‐state and time‐resolved fluorescence methods, as well as laser flash photolysis technique. In particular, the presence of anthryl and pyrenyl showed substantial enhancement on the singlet oxygen formation ability of BODIPY with up to 58 % and 34 % quantum efficiency, respectively, owing to their stronger electron‐donating ability. Upon the increase in singlet oxygen formation, the fluorescence quantum yield and lifetime values of the aryl‐BODIPY showed a concomitant decrease. The increase in solvent polarity enhances the singlet oxygen generation but decreases the fluorescence quantum yield. The results are explained by the presence of intramolecular photoinduced electron transfer from the aryl moiety to BODIPY core. This method of promoting T₁ formation is very different from the traditional heavy atom effect by I, Br, or transition metal atoms. This type of novel photosensitizers may find important applications in organic oxygenation reactions and photodynamic therapy of tumors.     

Dibenzo[a,j]phenazine‐Cored Donor–Acceptor–Donor Compounds as Green‐to‐Red/NIR Thermally Activated Delayed Fluorescence Organic Light Emitters

A new family of thermally activated delayed fluorescence (TADF) emitters based on U‐shaped D‐A‐D architecture with a novel accepting unit has been developed. All investigated compounds have small singlet‐triplet energy splitting (ΔE_ST) ranging from 0.02 to 0.20 eV and showed efficient TADF properties. The lowest triplet state of the acceptor unit plays the key role in the TADF mechanism. OLEDs fabricated with these TADF emitters achieved excellent efficiencies up to 16 % external quantum efficiency (EQE).     

Light-Harvesting Antenna and Proton-Activated Photodynamic Effect of a Novel BODIPY−Fullerene C60 Dyad as Potential Antimicrobial Agent

A covalently linked BODIPY−fullerene C₆₀ dyad (BDP−C₆₀) was synthesized as a two-segment structure, which consists of a visible light-harvesting antenna attached to an energy or electron acceptor moiety. This structure was designed to improve the photodynamic action of fullerene C₆₀ to inactivate bacteria. The absorption spectrum of BDP−C₆₀ was found to be a superposition of the spectra of its constitutional moieties, whereas the fluorescence emission of the BODIPY unit was strongly quenched by the fullerene C₆₀. Spectroscopic, calculations, and redox studies indicate a competence between photoinduced energy and electron transfer. Protonating the dimethylaminophenyl substituent through addition of an acidic medium led to a substantial increase in the fluorescence emission, triplet excited state formation, and singlet molecular oxygen production. At physiological pH, photosensitized inactivation of Staphylococcus aureus mediated by 1 μM BDP−C₆₀ exhibited a 4.5 log decrease of cell survival (>99.997 %) after 15 min irradiation. A similar result was obtained with Escherichia coli using 30 min irradiation. Moreover, proton-activated photodynamic action of BDP−C₆₀ turned this dyad into a highly effective photosensitizer to eradicate E. coli. Therefore, BDP−C₆₀ is an interesting photosensitizing structure in which the light-harvesting antenna effect of the BODIPY unit combined with the protonation of dimethylaminophenyl group can be used to improve the photoinactivation of bacteria.     

Tuning the singlet-triplet energy gap: a unique approach to efficient photosensitizers with aggregation-induced emission (AIE) characteristics

The efficiency of the intersystem crossing process can be improved by reducing the energy gap between the singlet and triplet excited states (ΔE _ST), which offers the opportunity to improve the yield of the triplet excited state. Herein, we demonstrate that modulation of the excited states is also an effective strategy to regulate the singlet oxygen generation of photosensitizers. Based on our previous studies that photosensitizers with aggregation-induced emission characteristics (AIE) showed enhanced fluorescence and efficient singlet oxygen production in the aggregated state, a series of AIE fluorogens such as TPDC, TPPDC and PPDC were synthesized, which showed ΔE _ST values of 0.48, 0.35 and 0.27 eV, respectively. A detailed study revealed that PPDC exhibited the highest singlet oxygen efficiency (0.89) as nanoaggregates, while TPDC exhibited the lowest efficiency (0.28), inversely correlated with their ΔE _ST values. Due to their similar optical properties, TPDC and PPDC were further encapsulated into nanoparticles (NPs). Subsequent surface modification with cell penetrating peptide (TAT) yielded TAT–TPDC NPs and TAT–PPDC NPs. As a result of the stronger singlet oxygen generation, TAT–PPDC NPs showed enhanced cancer cell ablation as compared to TAT–TPDC NPs. Fine-tuning of the singlet-triplet energy gap is thus proven to be an effective new strategy to generate efficient photosensitizers for photodynamic therapy.     

Ultrafast Photoinduced Energy and Electron Transfer in Multi‐Modular Donor–Acceptor Conjugates

New multi‐modular donor–acceptor conjugates featuring zinc porphyrin (ZnP), catechol‐chelated boron dipyrrin (BDP), triphenylamine (TPA) and fullerene (C₆₀), or naphthalenediimide (NDI) have been newly designed and synthesized as photosynthetic antenna and reaction‐center mimics. The X‐ray structure of triphenylamine‐BDP is also reported. The wide‐band capturing polyad revealed ultrafast energy‐transfer (k_ENT=1.0×10¹² s^?1) from the singlet excited BDP to the covalently linked ZnP owing to close proximity and favorable orientation of the entities. Introducing either fullerene or naphthalenediimide electron acceptors to the TPA‐BDP‐ZnP triad through metal–ligand axial coordination resulted in electron donor–acceptor polyads whose structures were revealed by spectroscopic, electrochemical and computational studies. Excitation of the electron donor, zinc porphyrin resulted in rapid electron‐transfer to coordinated fullerene or naphthalenediimide yielding charge separated ion‐pair species. The measured electron transfer rate constants from femtosecond transient spectral technique in non‐polar toluene were in the range of 5.0×10⁹–3.5×10¹⁰ s^?1. Stabilization of the charge‐separated state in these multi‐modular donor–acceptor polyads is also observed to certain level.     

Designing Efficient and Ultralong Pure Organic Room‐Temperature Phosphorescent Materials by Structural Isomerism

Pure organic materials with ultralong room‐temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, they generally show inefficient intersystem crossing (ISC) owing to weak spin–orbit coupling (SOC). A design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔE_ST) and pure ππ* configuration of the lowest triplet state (T₁) via structural isomerism was used to obtain efficient and ultralong RTP materials. The meta isomer of carbazole‐substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1 %. Study of the structure–property relationship shows that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔE_ST and pure ππ* configuration of T₁.     

Generation of “Sumanenylidene”: A Ground‐State Triplet Carbene on a Curved π‐Conjugated Periphery

We have observed the generation of sumanenylidene ( 2 ), a divalent, neutral‐carbon species at the benzylic position of sumanene ( 1 ). We also clarified both experimentally and theoretically that the ground state of compound 2 was a triplet state and that its singlet–triplet energy gap (ΔE_ST) was similar to that in fluorenylidene. The curved structure of compound 2 led to slightly better spin delocalization over the two adjacent aromatic rings than in planar systems, because of the unpaired spins on the σ and π orbitals. Synthetic application of the carbene precursor, diazosumanene ( 5 ), with a variety of thiocarbonyl compounds revealed its utility for the preparation of tetrasubstituted alkene compounds (e.g., that contain a strongly electron‐donating unit) that are directly conjugated to the sumanene ( 1 ) moiety.     

Molecular Design Strategy of Thermally Activated Delayed Fluorescent Emitters Using CN‐Substituted Imidazopyrazine as a New Electron‐Accepting Unit

Thermally activated delayed fluorescence (TADF)‐based organic light‐emitting diodes (OLEDs) have attracted enormous attention recently due to their capability to replace conventional phosphorescent organic light‐emitting diodes for practical applications. In this work, a newly designed CN‐substituted imidazopyrazine moiety was utilized as an electron‐accepting unit in a TADF emitter. Two TADF emitters, 8‐(3‐cyano‐4‐(9,9‐dimethylacridin‐10(9H)‐yl)phenyl)‐2‐phenylimidazo[1,2‐a]pyrazine‐3‐carbonitrile (Ac‐CNImPyr) and 8‐(3‐cyano‐4‐(10H‐phenoxazin‐10‐yl)phenyl)‐2‐phenylimidazo[1,2‐a]pyrazine‐3‐carbonitrile (PXZ‐CNImPyr), were developed based on the CN‐substituted imidazopyrazine acceptor combined with acridine and phenoxazine donor, respectively. A CN‐substituted phenyl spacer was introduced between the donor and acceptor for a sufficiently small singlet‐triplet energy gap (ΔE_ST) and molecular orbital management. Small ΔE_ST of 0.07 eV was achieved for the phenoxazine donor‐based PXZ‐CNImPyr emitter. As a result, an organic light‐emitting diode based on the PXZ‐CNImPyr emitter exhibited a high external quantum efficiency of up to 12.7 %, which surpassed the EQE limit of common fluorescent emitters. Hence, the CN‐modified imidazopyrazine unit can be introduced as a new acceptor for further modifications to develop efficient TADF‐based OLEDs.     

Modulation of Thermally Activated Delayed Fluorescence in Waterborne Polyurethanes via Charge‐Transfer Effect

Here, we designed several waterborne polyurethanes (WPUs) with efficient thermally activated delayed fluorescence (TADF) via serving charge‐transfer (CT) states as a mediate bridge between singlet and triplet states to boost reverse intersystem crossing (RISC). By tuning substituents of diphenyl sulfone (DS), we found that O,O′‐ and S,S′‐substituted DS covalently incorporated in WPUs solely show typical fluorescence emission with lifetimes in the nanosecond range. Interestingly, TADF appears by replacing the substituent with the nitrogen atom, of which lifetimes are up to ≈10 microseconds and ≈1 millisecond in air and vacuum, respectively, even though the energy gap between singlet and triplet states (ΔE_ST) is still large for generating TADF. To explain this phenomenon, an energy level mode based on CT states and an ³(n‐π*) receiver state was proposed. By the rational modulation of CT states, it is possible to tune the ΔE_ST to render TADF‐based materials suitable for versatile applications.     

A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker

Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H₂P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C₆₀‐X‐NH₂ (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀ with those of BDP‐H₂P, BDP‐ZnP and BDP‐C₆₀, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H₂P or ZnP. This is then followed by an electron transfer to C₆₀, yielding the formation of the singlet charge‐separated states, namely BDP‐H₂P ^.+‐ C₆₀ ^.? and BDP‐ZnP ^.+‐ C₆₀ ^{. ?}. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis.     

Accessing the Triplet State in Heavy‐Atom‐Free Perylene Diimides

Previous studies of perylenediimides (PDIs) mostly utilized the lowest singlet excited state S₁. Generation of a triplet excited state (T₁) in PDIs is important for applications ranging from photodynamic therapy to photovoltaics; however, it remains a formidable task. Herein, we developed a heavy‐atom‐free strategy to prompt the T₁←S₁ intersystem crossing (ISC) by introducing electron‐donating aryl (Ar) groups at the head positions of an electron‐deficient perylenediimide (PDI) core. We found that the ISC efficiency increases from 8 to 54 % and then to 86 % by increasing the electron‐donating ability of head‐substituted aryl groups from phenyl (p‐PDI) to methoxyphenyl (MeO‐PDI) and then to methylthioxyphenyl (MeS‐PDI). By enhancing the intramolecular charge‐transfer (ICT) interaction from p‐PDI to MeO‐PDI, and then to MeS‐PDI, singlet oxygen generation via energy‐transfer reactions from T₁ of PDIs to ³O₂ was demonstrated with the highest yield of up to 80 %. These results provide guidelines for developing new triplet‐generating PDIs and related rylene diimides for optoelectronic applications.     

“Two‐Point” Self‐Assembly and Photoinduced Electron Transfer in meso‐Donor‐Carrying Bis(styryl crown ether)‐BODIPY–Bis(alkylammonium)fullerene Donor–Acceptor Conjugates

BF₂‐chelated dipyrromethene, BODIPY, was functionalized to carry two styryl crown ether tails and a secondary electron donor at the meso position. By using a “two‐point” self‐assembly strategy, a bis‐alkylammonium‐functionalized fullerene (C₆₀) was allowed to self‐assemble the crown ether voids of BODIPY to obtain multimodular donor–acceptor conjugates. As a consequence of the two‐point binding, the 1:1 stoichiometric complexes formed yielded complexes of higher stability in which fluorescence of BODIPY was found to be quenched; this suggested the occurrence of excited‐state processes. The geometry and electronic structure of the self‐assembled complexes were derived from B3LYP/3‐21G(*) methods in which no steric constraints between the entities was observed. An energy‐level diagram was established by using spectral, electrochemical, and computational results to help understand the mechanistic details of excited‐state processes originating from ¹bis‐styryl‐BODIPY*. Femtosecond transient absorbance studies were indicative of the formation of an exciplex state prior to the charge‐separation process to yield a bis‐styryl‐BODIPY ^{. +}–C₆₀ ^{. −} radical ion pair. The time constants for charge separation were generally lower than charge‐recombination processes. The present studies bring out the importance of multimode binding strategies to obtain stable self‐assembled donor–acceptor conjugates capable of undergoing photoinduced charge separation needed in artificial photosynthetic applications.     

Rational Design of Emissive NIR‐Absorbing Chromophores: RhIII Porphyrin‐Aza‐BODIPY Conjugates with Orthogonal Metal–Carbon Bonds

The facile synthesis of Group 9 Rh^III porphyrin‐aza‐BODIPY conjugates that are linked through an orthogonal Rh?C(aryl) bond is reported. The conjugates combine the advantages of the near‐IR (NIR) absorption and intense fluorescence of aza‐BODIPY dyes with the long‐lived triplet states of transition metal rhodium porphyrins. Only one emission peak centered at about 720 nm is observed, irrespective of the excitation wavelength, demonstrating that the conjugates act as unique molecules rather than as dyads. The generation of a locally excited (LE) state with intramolecular charge‐transfer (ICT) character has been demonstrated by solvatochromic effects in the photophysical properties, singlet oxygen quantum yields in polar solvents, and by the results of density functional theory (DFT) calculations. In nonpolar solvents, the Rh^III conjugates exhibit strong aza‐BODIPY‐centered fluorescence at around 720 nm (Φ_F=17–34 %), and negligible singlet oxygen generation. In polar solvents, enhancements of the singlet‐oxygen quantum yield (Φ_Δ=19–27 %, λ_ex=690 nm) have been observed. Nanosecond pulsed time‐resolved absorption spectroscopy confirms that relatively long‐lived triplet excited states are formed. The synthetic methodology outlined herein provides a useful strategy for the assembly of functional materials that are highly desirable for a wide range of applications in material science and biomedical fields.     

Polymerization‐Enhanced Intersystem Crossing: New Strategy to Achieve Long‐Lived Excitons

For a singlet–triplet coupled molecular system, the efficiency of forward and reverse intersystem crossing processes can be enhanced by reducing the energy gap between the singlet and triplet excited states (ΔE_ST), thus prolonging the exciton lifetimes. This has been proven beneficial for many emerging applications such as molecular luminescence, optoelectronics, and photonics. Here, a strategy is proposed to create small ΔE_ST by polymerizing fluorescent dye molecules, the efficacy of which is justified by density functional theory calculations and ultrafast spectroscopy. Thus, singlet–triplet exciton communication through polymerization‐enhanced intersystem crossing is also proposed.

     

Aza‐BODIPY Derivatives: Enhanced Quantum Yields of Triplet Excited States and the Generation of Singlet Oxygen and their Role as Facile Sustainable Photooxygenation Catalysts

A new series of aza‐BODIPY derivatives ( 4 a – 4 c , 5 a , c , and 6 b , c ) were synthesized and their excited‐state properties, such as their triplet excited state and the yield of singlet‐oxygen generation, were tuned by substituting with heavy atoms, such as bromine and iodine. The effect of substitution has been studied in detail by varying the position of halogenation. The core‐substituted dyes showed high yields of the triplet excited state and high efficiencies of singlet‐oxygen generation when compared to the peripheral‐substituted systems. The dye 6 c , which was substituted with six iodine atoms on the core and peripheral phenyl ring, showed the highest quantum yields of the triplet excited state (Φ_T=0.86) and of the efficiency of singlet‐oxygen generation (Φ_Δ=0.80). Interestingly, these dyes were highly efficient as photooxygenation catalysts under artificial light, as well as under normal sunlight conditions. The uniqueness of these aza‐BODIPY systems is that they are stable under irradiation conditions, possess strong red‐light absorption (620–680 nm), exhibit high yields of singlet‐oxygen generation, and act as efficient and sustainable catalysts for photooxygenation reactions.     

Time‐Dependent Photodynamic Therapy for Multiple Targets: A Highly Efficient AIE‐Active Photosensitizer for Selective Bacterial Elimination and Cancer Cell Ablation

Pathogen infections and cancer are two major human health problems. Herein, we report the synthesis of an organic salt photosensitizer (PS), called 4TPA‐BQ, by a one‐step reaction. 4TPA‐BQ presents aggregation‐induced emission features. Owing to the aggregation‐induced reactive oxygen species generated and a sufficiently small ΔE_ST, 4TPA‐BQ shows a satisfactorily high ¹O₂ generation efficiency of 97.8 %. In vitro and in vivo experiments confirmed that 4TPA‐BQ exhibited potent photodynamic antibacterial performance against ampicillin‐resistant Escherichia coli with good biocompatibility in a short time (15 minutes). When the incubation duration persisted long enough (12 hours), cancer cells were ablated efficiently, leaving normal cells essentially unaffected. This is the first reported time‐dependent fluorescence‐guided photodynamic therapy in one individual PS, which achieves ordered and multiple targeting simply by varying the external conditions. 4TPA‐BQ reveals new design principles for the implementation of efficient PSs in clinical applications.     

A Novel BODIPY‐Based Low‐Band‐Gap Small‐Molecule Acceptor for Efficient Non‐fullerene Polymer Solar Cells

We report herein an efficient A¹‐C≡C‐A²‐C≡C‐A¹ type small‐molecule 4,4'‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐ indacene (BODIPY) acceptor (A¹=BODIPY and A²=diketopyrrolopyrrole (DPP)) by following the A‐to‐A excited electron delocalization via the BODIPY meso ‐position, the inherent directionality for the excited electron delocalization. The lowest unoccupied molecular orbital (LUMO) delocalizes across over whole the two flanking A¹ and the central A², and the highest occupied molecular orbital (HOMO) localizes dominantly on the ‐C≡C‐DPP‐C≡C‐ segment. The excited electron upon light excitation of the DPP segment delocalizes over both the BODIPY and DPP segments. The acceptor in chloroform shows an unprecedented plateau‐like broad absorption between 550 and 700 nm with a large FWHM value of 195 nm. Upon transition into solid film, the acceptor shows absorption in the whole near ultraviolet‐visible‐near infrared wavelength region (300‐830 nm) with a low band gap of 1.5 eV and a maximum absorptivity of 0.85×10⁵ cm^‐1. Introduction of the ethynyl spacer between the A¹ and A² and the close BODIPY‐to‐DPP LUMO energy levels are crucial for the excited π−electron delocalization across over whole the conjugation backbone. A power conversion efficiency of 6.60% was obtained from the ternary non‐fullerene solar cell with PTB7‐Th:p ‐DTS(FBTTh₂)₂ (0.5 : 0.5) as the donor materials, which is the highest value among the non‐fullerene organic solar cells with BODIPY as the electron acceptor material.     

Poly(L‐Glutamic Acid)‐Drug Conjugates for Chemo‐ and Photodynamic Combination Therapy

Despite the polymeric vascular disrupting agent (poly(_L‐glutamic acid)‐graft‐methoxy poly(ethylene glycol)/combretastatin A4) nanoparticles can efficiently inhibit cancer growth, their further application is still a challenge owing to the tumor recurrence and metastasis after treatment. In this study, two poly(_L‐glutamic acid)‐drug conjugates for chemo‐and photodynamic combination therapy are fabricated. PLG‐g‐mPEG‐CA4 nanoparticles are prepared by combretastatin A4 (CA4) and poly(_L‐glutamic acid)‐graft‐methoxy poly(ethylene glycol) (PLG‐g‐mPEG) using the Yamaguchi esterification reaction. PLG‐g‐mPEG‐TPP (TPP: 5, 10, 15, 20‐tetraphenylporphyrin) nanoparticles are constructed using PLG‐g‐mPEG and amine porphyrin through condensation reaction between carboxyl group of PLG‐g‐mPEG and amino group of porphyrin. The results showed that PLG‐g‐mPEG‐CA4 nanoparticles have good antitumor ability. PLG‐g‐mPEG‐TPP nanoparticles can produce singlet oxygen under the laser irradiation. Moreover, the combined therapy of PLG‐g‐mPEG‐CA4 and PLG‐g‐mPEG‐TPP nanoparticles has higher antitumor effect than the single chemotherapy or the single photodynamic therapy in vitro. The combination of CA4 nondrug and photodynamic therapy provides a new insight for enhancing the tumor therapeutic effect with vascular disrupting agents and other therapy.     

A New Heteroleptic Ruthenium(II) Polypyridyl Complex with Long‐Wavelength Absorption and High Singlet‐Oxygen Quantum Yield

Ruthenium(II) polypyridyl complexes with long‐wavelength absorption and high singlet‐oxygen quantum yield exhibit attractive potential in photodynamic therapy. A new heteroleptic Ru^II polypyridyl complex, [Ru(bpy)(dpb)(dppn)]²⁺ (bpy=2,2′‐bipyridine, dpb=2,3‐bis(2‐pyridyl)benzoquinoxaline, dppn=4,5,9,16‐tetraaza‐dibenzo[a,c]naphthacene), is reported, which exhibits a ¹MLCT (MLCT: metal‐to‐ligand charge transfer) maximum as long as 548 nm and a singlet‐oxygen quantum yield as high as 0.43. Steady/transient absorption/emission spectra indicate that the lowest‐energy MLCT state localizes on the dpb ligand, whereas the high singlet‐oxygen quantum yield results from the relatively long ³MLCT(Ru→dpb) lifetime, which in turn is the result of the equilibrium between nearly isoenergetic excited states of ³MLCT(Ru→dpb) and ³ππ*(dppn). The dppn ligand also ensures a high binding affinity of the complex towards DNA. Thus, the combination of dpb and dppn gives the complex promising photodynamic activity, fully demonstrating the modularity and versatility of heteroleptic Ru^II complexes. In contrast, [Ru(bpy)₂(dpb)]²⁺ shows a long‐wavelength ¹MLCT maximum (551 nm) but a very low singlet‐oxygen quantum yield (0.22), and [Ru(bpy)₂(dppn)]²⁺ shows a high singlet‐oxygen quantum yield (0.79) but a very short wavelength ¹MLCT maximum (442 nm).