Large-Area Fabrication of Hexaazatrinaphthylene-Based 2D Metal-Organic Framework Films for Flexible Photodetectors and Optoelectronic Synapses.

2D conjugated metal-organic frameworks (c-MOFs) have emerged as promising materials for (opto)electronic applications due to their excellent charge transport properties originating from the unique layered-stacked structures with extended in-plane conjugation. The further advancement of MOF-based (opto)electronics necessitates the development of novel 2D c-MOF thin films with high quality. Cu-HHHATN (HHHATN: hexahydroxyl-hexaazatrinaphthylene) is a recently reported 2D c-MOF featuring high in-plane conjugation, strong interlayer π-π stacking, and multiple coordination sites, while the production of its thin-film form has not yet been reported. Herein, large-area Cu-HHHATN thin films with preferential orientation, high uniformity, and smooth surfaces are realized by using a convenient layer-by-layer growth method. Flexible photodetectors are fabricated, showing broadband photoresponse ranging from UV to short-wave infrared (370 to 1450 nm). The relatively long relaxation time of photocurrent, which arises from the trapping of photocarriers, renders the device's synaptic plasticity similar to that of biological synapses, promising its use in neuromorphic visual systems. This work demonstrates the great potential of Cu-HHHATN thin films in flexible optoelectronic devices for various applications.

In situ Electropolymerized 3D Microporous Cobalt-Porphyrin Nanofilm for Highly Effective Molecular Electrocatalytic Reduction of Carbon Dioxide.

Electrocatalytic CO2 reduction reaction (CO2 RR) based on molecular catalysts, for example, cobalt porphyrin, is promising to enhance the carbon cycle and mitigate current climate crisis. However, the electrocatalytic performance and accurate evaluations remain problems because of either the low loading amount or the low utilization rate of the electroactive CoN4 sites. Herein a monomer is synthesized, cobalt(II)-5,10,15,20-tetrakis(3,5-di(thiophen-2-yl)phenyl)porphyrin (CoP), electropolymerized onto carbon nanotubes (CNTs) networks, affording a molecular electrocatalyst of 3D microporous nanofilm (EP-CoP, 2-3 nm thickness) with highly dispersed CoN4 sites. The new electrocatalyst shortens the electron transfer pathway, accelerates the redox kinetics of CoN4 sites, and improves the durability of the electrocatalytic CO2 RR. From the intrinsic redox behavior of CoN4 sites, the effective utilization rate is obtained as 13.1%, much higher than that of the monomer assembled electrode (5.8%), and the durability is also promoted dramatically (>40 h) in H-type cells. In commercial flow cells, EP-CoP can achieve a faradic efficiency for CO (FECO ) over 92% at an overpotential of 160 mV. At a higher overpotential of 620 mV, the working current density can reach 310 mA cm-2 with a high FECO of 98.6%, representing the best performance for electrodeposited molecular porphyrin electrocatalysts.

Tetrazolyl Porphyrin-Based Hydrogen-Bonded Organic Frameworks: Active Sites-Mediated Host-Guest Synergy for Advanced Antimicrobial Applications.

Hydrogen-bonded organic frameworks (HOFs) with multiple functions and permanent pores have received widespread attention due to their potential applications in gas adsorption/separation, drug delivery, photocatalysis, proton conduction, and other fields. Herein, we constructed a three-dimensional (3D) HOF with 1D square channels by utilizing a dual-functional tetrazolyl porphyrin ligand bearing an active center of the porphyrin core and open sites of nitrogen atoms through π-π stacking and hydrogen-bonding interaction self-assembly. The structure exhibits both solvent resistance and thermal stability, and especially, maintains these after being transformed into nanoparticles. Meanwhile, the active sites exposed on the inner wall of the pores can interact well with the photoactive cationic dye molecules to form an effective host-guest (H-G) system, which can realize boosted photosensitized singlet oxygen (1O2) production under red light irradiation and synergistic sterilization toward Staphylococcus aureus (S. aureus) with an inhibition ratio as high as 99.9%. This work provides a valuable design concept for HOF-related systems in pursuit of promoted photoactivity.

Small Molecules Containing Amphoteric Imidazole Motifs as Sensitizers for Dye-Sensitized Solar Cells: An Overview.

Organic dyes, porphyrins and inorganic complexes containing imidazole (IM) motifs have been demonstrated as a new class of sensitizers in dye-sensitized solar cells (DSSCs). Particularly, the amphoteric nature of IM-based motifs allows them to be used as donors (D), auxiliary donors (DA), linker/branch (π), or acceptors (A) in D-π-A-based organic dyes and porphyrins and also employed as cyclometalated heteroleptic and ancillary ligands in the Ru(II) and Ir(III) complexes for DSSCs. It is noteworthy that the introduction of IM chromophores in the dyes of D-π-A configuration can improve the light-harvesting properties and prohibit the charge recombination reactions due to the extension of the π-conjugated structures and hydrophobic nature. Similarly, in the case of inorganic complexes, the presence of IM motifs as ligands can improve the light-harvesting ability, give facilely tuned HOMO and LUMO energy levels, increase the charge recombination resistance and photostability. This results in enhanced photocurrent (JSC) and photovoltage (VOC) and consequently solar-to-power conversion efficiency (η) of DSSC devices based on Ru(II) and Ir(III) complexes. Considering the interesting DSSC applications of IM-derived molecules, in this review, we therefore comprehensively discuss their photophysical, electrochemical and photovoltaic properties reported so far and establish their structure-activity relationship to further advance the η of DSSCs. To the best of our knowledge, there is no such a review interpreting the importance of molecules possessing IM-motifs for DSSC applications to date.

Dually Modified Wide-Bandgap Perovskites by Phenylethylammonium Acetate toward Highly Efficient Solar Cells with Low Photovoltage Loss.

Wide-bandgap perovskites as a class of promising top-cell materials have shown great promise in constructing efficient perovskite-based tandem solar cells, but their intrinsic relatively low radiative efficiency results in a large open-circuit voltage (VOC) deficit and thereby limits the whole device performance. Reducing film flaws or optimizing interfacial energy level alignments in wide-bandgap perovskite devices can efficiently inhibit nonradiative recombination to boost device VOC and efficiency. However, the simultaneous regulation on both sides and their underlying mechanism are less explored. Herein, a bifunctional modification approach is proposed to optimize the wide-bandgap perovskite surface with an ultrathin layer of phenylethylammonium acetate (PEAAc) to synchronously decrease the surface imperfection and mitigate the interfacial energy barrier. This treatment effectively heals under-coordinated surface defects through the formation of chemical interaction between the perovskite and PEAAc, bringing about a much slower charge trapping process and dramatically decreasing nonradiative recombination losses. Meanwhile, the passivation-induced upshifted Fermi level of the perovskite contributes to accelerated electron extraction and larger Fermi-level splitting under illumination. Consequently, the PEAAc-modified wide-bandgap (1.68 eV) device achieves an optimal efficiency of 20.66% with a high VOC of 1.25 V, among the highest reported VOC values for wide-bandgap perovskite devices, enormously outperforming that (18.86% and 1.18 V) of the device without passivation. In addition, the radiative limit of VOC for both cells is determined to be 1.42 V, delivering nonradiative recombination losses of 0.24 and 0.17 V for the control and PEAAc-modified devices, respectively. These results highlight the significance of the bifunctional modification strategy in achieving high-performance wide-bandgap perovskite devices.

Correction to Covalent Triazine Frameworks Embedded with Ir Complexes for Enhanced Photocatalytic Hydrogen Evolution.

[This corrects the article DOI: 10.1021/acsaem.2c00977.].

2D Metal-Organic Framework Cu3 (HHTT)2 Films for Broadband Photodetectors from Ultraviolet to Mid-Infrared.

Cu3 (HHTT)2 (HHTT: 2,3,7,8,12,13-hexahydroxytetraazanaphthotetraphene) is a novel 2D conjugated metal-organic framework (2D c-MOF) with efficient in-plane d-π conjugations and strong interlayer π-π interactions while the growth of Cu3 (HHTT)2 thin films has never been reported until now. Here, the successful fabrication of highly oriented wafer-scale Cu3 (HHTT)2 thin films with a layer-by-layer growth method on various substrates is presented. Its semiconducting behavior and carrier transport mechanisms are clarified through temperature and frequency-dependent conductivity measurements. Flexible photodetectors based on Cu3 (HHTT)2 thin films exhibit reliable photoresponses at room temperature in a wavelength region from UV to mid-IR, which is much broader than those of solution-processed broadband photodetectors reported previously. Moreover, the photodetectors can show a typical synaptic behavior and excellent data recognition accuracy in artificial neural networks. This work opens a window for the exploration of high-performance and multifunctional optoelectronic devices based on 2D c-MOFs.

Water-Stable Nickel Metal-Organic Framework Nanobelts for Cocatalyst-Free Photocatalytic Water Splitting to Produce Hydrogen.

Development of water-stable metal-organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear a wide range of pH environment in aqueous solution. Both experimental and theoretical results indicate a feasible electron transfer from the H4TBAPy ligand (light-harvesting center) to the Ni-O cluster node (catalytic center), on which water splitting to produce hydrogen can be efficiently driven free of cocatalyst. Compared to the single crystal, the exfoliated two-dimensional (2D) nanobelts show more efficient charge separation due to its shortened charge transfer distance and remarkably enhanced active surface areas, resulting in 164 times of promoted water reduction activity. The optimal H2 evolution rate on the nanobelt reaches 98 µmol h-1 (ca. 5 mmol h-1 g-1) showing benchmarked apparent quantum efficiency (AQE) of 8.0% at 420 nm among water-stable MOFs photocatalysts.

Organic Nanoparticles Based on D-A-D Small Molecule: Self-Assembly, Photophysical Properties, and Synergistic Photodynamic/Photothermal Effects.

Cancer is one of the major diseases threatening human health. Traditional cancer treatments have notable side-effects as they can damage the immune system. Recently, phototherapy, as a potential strategy for clinical cancer therapy, has received wide attention due to its minimal invasiveness and high efficiency. Herein, a small organic molecule (PTA) with a D-A-D structure was prepared via a Sonogashira coupling reaction between the electron-withdrawing dibromo-perylenediimide and electron-donating 4-ethynyl-N,N-diphenylaniline. The amphiphilic organic molecule was then transformed into nanoparticles (PTA-NPs) through the self-assembling method. Upon laser irradiation at 635 nm, PTA-NPs displayed a high photothermal conversion efficiency (PCE = 43%) together with efficient reactive oxygen species (ROS) generation. The fluorescence images also indicated the production of ROS in cancer cells with PTA-NPs. In addition, the biocompatibility and photocytotoxicity of PTA-NPs were evaluated by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and live/dead cell co-staining test. Therefore, the as-prepared organic nanomaterials were demonstrated as promising nanomaterials for cancer phototherapy in the clinic.

Effects of Side-Chain Engineering with the S Atom in Thieno[3,2-b]thiophene-porphyrin to Obtain Small-Molecule Donor Materials for Organic Solar Cells.

To explore the effect of the introduction of heteroatoms on the properties of porphyrin materials, a new porphyrin-based derivative small-molecule donor named as PorTT-T was designed and synthesized based on alkyl-thieno[3,2-b]thiophene(TT)-substituted porphyrins. The linker bridge and end groups of PorTT-T were the same as those of XLP-II small-molecule donor materials, while the side-chain attached to the core of thieno[3,2-b]thiophene(TT)-substituted porphyrin was different. Measurements of intrinsic properties showed that PorTT-T has wide absorption and appropriate energy levels in the UV-visible range. A comparison of the morphologies of the two materials using atomic force microscopy showed that PorTT-T has a better surface morphology with a smaller root-mean-square roughness, and can present closer intermolecular stacking as compared to XLP-II. The device characterization results showed that PorTT-T with the introduced S atom has a higher open circuit voltage of 0.886 eV, a higher short circuit current of 12.03 mAcm-2, a fill factor of 0.499, a high photovoltaic conversion efficiency of 5.32%, better external quantum efficiency in the UV-visible range, and higher hole mobility.

Largely Color-Tuning Prompt and Delayed Fluorescence: Dinuclear Cu(I) Halide Complexes with tert-Amines and Phosphines.

Luminescent copper(I) halide complexes with bi- and tridentate rigid ligands have gained wide research interests. In this paper, six tetracoordinate dinuclear copper(I) halide complexes, Cu2X2(ppda)2 [ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline, X = I (1), Br (2), Cl (3)] and Cu2X2(pfda)2 [pfda = 2-[2-(dimethylamino)-4-(trifluoromethyl)phenyl(phenyl)phosphino]-N,N-dimethyl-5-trifluoromethylaniline, X = I (4), Br (5), Cl (6)], were successfully prepared and systematically characterized on their structures and photophysical properties. Complexes 1-5 have a centrosymmetric form with a planar Cu2X2 unit, and complex 6 has a mirror symmetry form with a butterfly-shaped Cu2X2. Solid complexes 1, 4, and 5 emit delayed fluorescence at room temperature, intense blue to greenish yellow (λmax = 443-570 nm) light, and their peak wavelengths are located at 443-570 nm with microsecond lifetimes (τ = 0.4-19.2 µs, ΦPL = 0.05-0.48). Complexes 2, 3, and 6 show prompt fluorescence, very weak yellowish green to yellow (λmax = 534-595 nm) emission with peak wavelengths at 534-595 nm, and lifetimes in nanoseconds (τ = 4.4-9.3 ns, ΦPL < 0.0001). (Metal + halide) to ligand and intraligand charge transitions are the main origin of the emission of the complexes. Solution-processed, complex-4-based nondoped and doped devices emit yellow green light with CIE coordinated at (0.41, 0.51), a maximum EQE up to 0.17%, and luminance reaching 75.52 cd/m2.

A novel chemosensor for the distinguishable detections of Cu2+ and Hg2+ by off-on fluorescence and ratiometric UV-visible absorption.

A novel dual-functional chemosensor, derived from the conjugation of rhodamine B with a quinoline derivative (RHQ), was firstly synthesized with high efficiency and cost-effectiveness for the distinguishable detections of Cu2+ and Hg2+ via ring-opening and ring-forming mechanism. The chemosensor exhibits highly selective and distinguishable responses for Cu2+ and Hg2+ in CH3CN-H2O (4:1, v/v) with off-on fluorescence and ratiometric ultraviolet-visible (UV-Vis) absorption changes. Additionally, Cu2+ is identified by opening a rhodamine spirocycle with a UV-Vis absorption band, at around 560 nm and fluorescence turn-on. Interestingly, Hg2+ is discerned by opening the rhodamine spirocycle and by generating a new special cycle for the quinoline unit. Resultantly, there were two UV-Vis absorption bands at around 365 nm and 560 nm, which were accompanied by fluorescence turn-on. Moreover, the chemosensor can quantitatively detect Cu2+ and Hg2+ by off-on fluorescence and ratiometric UV-Vis absorption changes, respectively. Furthermore, the chemosensor with low cytotoxicity could be successfully administered to monitor Cu2+ and Hg2+ in living cells. This work may pay the way for the development of dual-functional chemosensor for quantificationally detecting metal ions in environmental and biological systems.

Donor-acceptor covalent organic frameworks of nickel(II) porphyrin for selective and efficient CO2 reduction into CO.

Donor-acceptor two-dimensional covalent organic frameworks, PD-COF-23 and PD-COF-23-Ni, are constructed and applied for selective CO2 reduction with CO conversion rates of 20.9 µmol g-1 h-1 and 40.0 µmol g-1 h-1, respectively, in the absence of any additional photosensitizers and noble metal co-catalysts within an operation time of 25 h. The multilayer nanosheet structure, efficient charge separation and transport, and internal reductive quenching cycle of the NiTAPP fragments of PD-COF-23-Ni result in its higher photocatalytic efficiency than that of PD-COF-23.

Side-Chain Engineering of Benzodithiophene-Bridged Dimeric Porphyrin Donors for All-Small-Molecule Organic Solar Cells.

Two new A-D-A small-molecule donors (C8T-BDTDP and C8ST-BDTDP) are prepared from benzodithiophene (BDT)-linked dimeric porphyrin (DP), which differ in side chains of BDT linkers with 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene (C8T-BDT) for the former and 4,8-bis{5-[(2-ethylhexyl)thio]-2-thienyl}benzo[1,2-b:4,5-b']dithiophene (C8ST-BDT) for the latter. Both dimeric porphyrin donors show strongly UV-visible to near-infrared absorption. Compared to C8T-BDTDP, C8ST-BDTDP with an alkylthiothienyl-substituted BDT linker exhibits more intense absorption bands in the film and a lower highest occupied molecular orbital energy level. The blend film of the electron acceptor 6TIC with the respective dimeric porphyrin donor displays a broad photon response from 400 to 900 nm, unfortunately, with an absorption valley at ca. 600 nm. The device based on C8ST-BDTDP/6TIC demonstrates a promising power conversion efficiency (PCE) of 10.39% with a high short-circuit current density (JSC) of 19.53 mA cm-2, whereas the device based on C8T-BDTDP/6TIC shows a slightly lower PCE of 8.73% with a JSC of 17.75 mA cm-2. The better performance for C8ST-BDTDP/6TIC is mainly attributed to efficient charge dissociation and transportation because of the smooth surface morphology and highly ordered crystalline packing.

Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production.

We employ facile aromatic nucleophilic substitution between the mercapto (-SH) and arylfluoro (Ar-F) groups to achieve extensive and robust cross-linking of a coordination host by porphyrin guests that also serve the purpose of versatile postsynthetic functionalization. For this, a tritopic linker with three trident-like thiol-flanked carboxyl units are reacted with ZrOCl2·8H2O to afford a two-dimensional (3,6-connected) net. The wide aperture of the porous framework solid, together with its stability in both air and boiling water, facilitates the entry of bulky metalloporphyrin guests and the subsequent property studies. On the porphyrin side, four pentafluorophenyl (C6F5-) groups offer multiple fluoro groups to facilitate their replacement by the thiol groups from the host net. The inserted metalloporphyrin bridges impart to the metal-organic framework (MOF) host stable and recyclable activities for photocatalytic hydrogen production. We also disclose an improvement in synthetic methodology, in which BBr3 is used to simultaneously cleave the ester and benzyl thioether groups to more efficiently access thiol-equipped carboxylic acid building block.

Multifunctional theranostic nanosystems enabling photothermal-chemo combination therapy of triple-stimuli-responsive drug release with magnetic resonance imaging.

Theranostic nanosystems are emerging as a promising approach for controlled drug delivery, diagnosis and multimodal therapeutics. Herein, a multifunctional theranostic nanoplatform is reported for photothermal-chemo combination therapy functioned with magnetic and thermal imaging. Hyaluronic acid (HA) coated Fe3O4@polydopamine nanoparticles equipped with redox-sensitive disulfide linkers have been subsequently deposited with an anticancer drug, doxorubicin (DOX) (termed as FPCH-DOX NPs). These nanocomposites possess an average diameter of 120 nm, a saturation magnetization of 28.5 emu g-1, DOX loading capacity of 7.13% and a transverse relaxation rate of 171.76 mM-1 s-1. The drug release could be triggered by pH, glutathione (GSH) concentration and light irradiation. Prussian blue staining and confocal microscopy demonstrate that these nanoplatforms have improved biocompatibility and cellular uptake in CD44-positive HeLa cell lines rather than in CD44-negative NIH 3T3 normal cell lines. In vitro evaluations demonstrate that the combination therapy of FPCH-DOX NPs lowers the cell viability to 16.2%, less than that of individual chemotherapy (55.3%) or PTT (52.1%). In vivo MRI indicates that the tumor accumulation of FPCH-DOX NPs provides enhanced MRI contrast, and in vivo thermal imaging verified their localized photothermal conversion effect in tumor tissues. Importantly, FPCH-DOX NPs present remarkable anti-tumor efficacy by photothermal-chemo combination therapy. H&E and Ki67 staining tests show obvious necrosis and weak cell proliferation at the region of the tumor. Thus, FPCH-DOX NPs are promising multifunctional nanoplatforms for highly effective cancer theranostics.

Two new bioactive diterpenes identified from Isodon interruptus.

In the course of our ongoing studies to discover bioactive chemical constituents from plants in the genus Isodon, two new diterpenes, kunminolide A (1) and rabdokunmin F (2) were isolated from the leaves of the medicinal plant Isodon interruptus. Kunminolide A (1) is a novel abietane-like diterpene with a novel skeleton, herein designated as 9, 10-seco-neoabietane. Rabdokunmin F (2) is an ent-kaurene diterpene with C-18 oxidized to a carboxylic acid group. The structures were determined by spectroscopic means including analysis of 1D- and 2D-NMR spectral data. Crystals of 1 obtained from methanol were suitable for X-ray analysis, which confirmed the chemical structure. Kunminolide A (1) demonstrated chemopreventive potential by inducing QR1 activity with a CD value of 14.3 µM, and rabdokunmin F (2) was found to have cytotoxic activities with IC50 values in the range of 1.1-3.0 µM.

Facile Preparation of Phthalocyanine-Based Nanodots for Photoacoustic Imaging and Photothermal Cancer Therapy In Vivo.

The development of near-infrared (NIR)-absorbing nanoagents for personalized multifunctional phototheranostics has attracted considerable attention in the past decade. Recently, the organic nanomaterials with good biosafety are considered as promising phototheranostic agents, while their facile synthesis remains challenging. Inspired by the preparation of carbon nanodots, we fabricate the NIR-absorbing phthalocyanine-based nanodots (ZnPc-NDs) using a facile method for multifunctional phototheranostics. The significant aggregation of phthalocyanines in nanodots induces a complete fluorescence quenching, which affords a high photothermal conversion efficiency (η = 45.7%). The ZnPc-NDs disperse very well in water media with an average diameter around 80 nm. Further conjugation of biotin on the surface of ZnPc-NDs affords tumor-targeting phthalocyanine nanodots (ZnPc-BT). The ZnPc-BT are demonstrated with favorable biocompatibility, intense photoacoustic signals, high tumor accumulation, and effective tumor suppression in vivo. This Article provides a new insight for further developing nanomedicines with imaging and therapeutic functions to treat cancers precisely and effectively.

A Simple Strategy to Fabricate Phthalocyanine-Encapsulated Nanodots for Magnetic Resonance Imaging and Antitumor Phototherapy.

Photothermal agents can transfer the absorbed light to heat energy, offering a noninvasive and controllable method to kill tumor cells and tissues. Here, we develop a simple and high-output strategy to prepare photothermal nanodots (MnPc-NDs) by the self-assembly and carbonization of manganese phthalocyanine. The aggregation of phthalocyanine molecules in the nanodots induces an efficient photothermal conversion. Thanks to the high thermal stability of phthalocyanine, the macrocycle is well preserved in the core of nanodots under the controlled hydrothermal temperature. Moreover, the as-prepared MnPc-NDs disperse well in aqueous solution with an average nanoscale size around 60 nm. The intense absorption in near-infrared (NIR) region, along with efficient reactive oxygen generation, high photothermal conversion efficiency (η = 59.8%), and excellent magnetic resonance contrast performances of MnPc-NDs endow them with great potential for MRI-guided cancer phototherapy. Therefore, the contribution provides a facile way to develop theranostic MnPc-NDs for precise and efficient cancer imaging and therapy.

Multifunctional theranostic agents based on prussian blue nanoparticles for tumor targeted and MRI-guided photodynamic/photothermal combined treatment.

The independence of photodynamic or photothermal modality create difficulties in the success of tumor therapy. In this current study, a multifunctional nanotheranostic agent of PDE-Ce6-HA was developed for tumor targeted and MRI-guided photodynamic/photothermal combined therapy (PDT/PTT). For this purpose, the near-infrared-absorbing nanoparticles of prussian blue were coated with polydopamine and successively conjugated with chlorin e6 (Ce6) for reactive oxygen species (ROS) generation. The resultant nanoparticles, denoted as PDE-Ce6, were then modified with hyaluronic acid (HA) through electrostatic interaction to yield the final therapeutic agent of PDE-Ce6-HA NPs. PDE-Ce6-HA NPs not only exhibited high colloid stability, good biocompatibility and suitable transverse relaxation rate (0.54 mM-1 s-1), but also high photothermal conversion efficiency (40.4%) and excellent ROS generation efficiency under NIR light irradiation. The confocal microscopy images demonstrated a selective uptake of PDE-Ce6-HA by CD44 overexpressed HeLa cells via HA-mediated endocytosis. Meanwhile, in vitro anti-cancer evaluation verified the significant photodynamic and photothermal combined effects of PDE-Ce6-HA on cancer cells. Moreover, PDE-Ce6-HA led to an increase of T1-MRI contrast in tumor site. Furthermore, in vivo anti-tumor evaluation proved that the PDE-Ce6-HA under both 808 and 670 nm laser showed significantly high tumor growth inhibition effects compared with individual PTT or PDT. Hence, PDE-Ce6-HA is applicable in tumor targeted and MRI-guided photodynamic/photothermal combined treatment.