Heavy Atom Effect Research Articles

Molecular Engineering for High-Performance X-ray Scintillators.

X-ray scintillators, materials that convert high-energy radiation into detectable light in the ultraviolet to visible spectrum, are widely used in industrial and medical applications. Organic and organic-inorganic hybrid systems have emerged as promising alternatives for X-ray detection and imaging due to their mechanical flexibility, lightweight, tunable excited states, and solution processability for large-scale fabrication. However, these systems often suffer from weak X-ray absorption and insufficient exciton utilization, which seriously affects their scintillation performance, limiting their potential for broader application and commercialization. This review highlights recent advances in molecular engineering for developing high-performance X-ray scintillators. Itfocuses on molecular design principles, such as the heavy atom effect, donor-acceptor/host-guest strategies, hydrogen/halogen bonding, molecular sensitization, and crystal packing, for enhancing scintillation performance. By leveraging these approaches, researchers have made significant strides in improving X-ray scintillation efficiency and advancing the potential of these materials for commercial applications.

Halogen Impact on the Supramolecular Organization of Chiral Phthalimide Emitters Displaying Room Temperature Phosphorescence.

Room temperature phosphorescence from organic materials has attracted an increasing attention in the recent years due to their potential application in various advancing technologies, notably in bioimaging and displays. In this context, heavy atoms such as halogen ones revealed useful tools to enhance the spin-orbit coupling (SOC) of molecular organic phosphors. However, the effect of halogen at the supramolecular level remains less understood, especially in the field of molecular crystals where additional factors can impact the phosphorescence emission. Here, we investigate external effect of halogens on the phosphorescence of chiral phthalimides molecular crystals. The results show that changing the nature of the halogen atom onto the phthalimide core leads to an evolution of the photophysical properties of the materials which does not necessarily follow the classical trend imposed by the expected internal heavy atom effect. Beyond this aspect, we showed that the halogen atom has a profound impact on the packing between the chromophores at the supramolecular level which is of paramount importance towards the optical properties (PLQY and lifetimes) of the different phosphors examined.

Ultralong Room-Temperature Phosphorescence in Ca(II) Metal-Organic Frameworks Based on Nicotinic Acid Ligands.

In recent years, metal-organic framework (MOF) materials with long persistent luminescence (LPL) have inspired extensive attention and presented various applications in security systems, information anticounterfeiting, and biological imaging fields. However, obtaining LPL materials with ultralong lifetime remains challenging. Halogen atoms, as nonmetallic elements existing in the frameworks, can not only induce the heavy-atom effect, effectively enhancing spin-orbit coupling and promoting intersystem crossing (ISC) processes, but also suppress non-radiative transition of the triplet states through the intra- and intermolecular interactions. Specifically, fluorine atoms with the strongest electronegativity may form intermolecular aggregate interlockings through halogen-bonding interactions that restrict molecular motions and vibrations, thereby improving phosphorescent lifetime. With the aforementioned considerations, two distinct types of MOFs with/without fluorine atoms (namely, Ca-MOF and 5FCa-MOF) were synthesized. Notably, by introducing fluorine atoms into MOFs, fluorine-induced intermolecular aggregate interlockings effectively enhanced the phosphorescent lifetime of 5FCa-MOF exceeding 264 ms compared to that of Ca-MOF (103.94 ms). Remarkably, both MOFs displayed bright LPL to the naked eye after removal of the irradiation source, especially 5FCa-MOF which can last for about 2 s. By introducing fluorine atoms, 5FCa-MOF exhibits greatly enhanced ISC with a rate constant up to 4.1 × 106 s-1 and suppressed non-radiative decay down to 3.73 s-1, thereby extending the LPL time. The thus obtained LPL provides potential in information encryption, security systems, optical anticounterfeiting, and so on.

Highly Efficient Red/Near‐Infrared Phosphorescence from Doped Crystals

AbstractOrganic red/near‐infrared (NIR) room temperature phosphorescence (RTP) materials with low toxicity and facile synthesis are highly sought after, particularly for applications in biotechnology and encryption. However, achieving efficient red/NIR RTP emitters has been challenging due to the weak spin‐orbit coupling of organics and the rapid nonradiative decay imposed by the energy gap law. Here we demonstrate highly efficient red/NIR RTP with boosted quantum yields (Φps) of up to 32.96 % through doping the thionated derivatives of phthalimide (PAI) (MTPAI and DTPAI) into PAI crystals. The red‐shifted photoluminescence (PL) stems from a combination of the external heavy atom effect and the formation of emissive clusters centered around electron‐rich sulfur atoms. Furthermore, the dopants enhance exciton generation efficiency and facilitate energy transfer from smaller PAI units to larger aggregates, leading to dramatically increased Φp. This strategy proves universal, opening possibilities for acquiring long‐wavelength RTP with tunable photophysical properties. The doped crystals exhibit promising applications in optical waveguides and encryption paper/ink. This research provides a practical approach to obtaining long‐wavelength RTP materials and offers valuable insights into the mechanisms governing host‐guest systems.

Highly Efficient Red/Near-Infrared Phosphorescence from Doped Crystals.

Organic red/near-infrared (NIR) room temperature phosphorescence (RTP) materials with low toxicity and facile synthesis are highly sought after, particularly for applications in biotechnology and encryption. However, achieving efficient red/NIR RTP emitters has been challenging due to the weak spin-orbit coupling of organics and the rapid nonradiative decay imposed by the energy gap law. Here we demonstrate highly efficient red/NIR RTP with boosted quantum yields (Φps) of up to 32.96 % through doping the thionated derivatives of phthalimide (PAI) (MTPAI and DTPAI) into PAI crystals. The red-shifted photoluminescence (PL) stems from a combination of the external heavy atom effect and the formation of emissive clusters centered around electron-rich sulfur atoms. Furthermore, the dopants enhance exciton generation efficiency and facilitate energy transfer from smaller PAI units to larger aggregates, leading to dramatically increased Φp. This strategy proves universal, opening possibilities for acquiring long-wavelength RTP with tunable photophysical properties. The doped crystals exhibit promising applications in optical waveguides and encryption paper/ink. This research provides a practical approach to obtaining long-wavelength RTP materials and offers valuable insights into the mechanisms governing host-guest systems.

BODIPY Photosensitizers Functionalized with Mannose for Fluorescence Cell-imaging and Photodynamic Therapy

The synthesis of four water-soluble mannose-tethering BODIPY-based photosensitizers (PSs) with varying substituents (-H, -OMe, -NO2 and -I) in the para-phenyl moiety attached to the meso-position of the BODIPY core, offering tumor-targeting and photodynamic therapeutic (PDT) potentials, is reported. The PDT capability of the synthesized PSs was investigated using the cervical cancer cell line HeLa. Owing to the heavy atom effect, BODIPY I, enhanced the intersystem crossing (ISC) to produce singlet oxygen (1O2) and maintained a high fluorescence quantum yield (ΦF) of 0.71. In contrast, the electron-donating methoxy substituent (BODIPY OMe) caused a notable perturbation in the occupied frontier molecular orbitals, subsequently achieving a higher 1O2 generation capability with a high ΦF of 0.85. Conversely, substitution with the electron-withdrawing nitro group (BODIPY NO2) resulted in a perturbation of unoccupied frontier molecular orbitals and generated a forbidden dark S1 state, negatively affecting both fluorescence and 1O2 generation efficiencies. The cytotoxicity of the synthesized water-soluble BODIPY PSs in the dark and under LED irradiation against the HeLa cell line was also assessed, with BODIPY I, OMe and H showing favorable PDT activity. Collectively, the performance of the mannose-conjugated BODIPY PSs in this study contributed promising results for the development of photodynamic therapeutic agents for cancer treatment.

Regulation of TADF and RTP Dual Emission via Internal and External Heavy-Atom Effects.

Organic materials with thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) dual emission have attracted great attention in recent years, but the regulation mechanism via internal and external heavy atoms is not clear enough. Here, we carry out a systematic theoretical investigation on the photophysical properties of the materials by introducing aliphatic or aromatic bromine atoms. The molecule with aromatic bromine atoms exhibits obvious TADF owing to the effective reverse intersystem crossing (RISC) with matchable energy levels and enhanced spin orbit couplings, the molecule with aliphatic bromine atoms shows a long RTP lifetime because of the reduced nonradiative transition of triplet excitons, and the molecule with both aliphatic and aromatic bromine atoms presents balanced TADF and RTP emissions thanks to the synergy internal and external heavy-atom effects. Besides, the internal and external heavy atoms induce multisite intermolecular interactions, effectively suppressing the nonradiative process in the solid phase. The efficient RISC process and the suppressed nonradiative process of triplet excitons should be key to regulating the dual emission property. These findings and insights are of great importance for revealing the structure-performance relationship, providing theoretical guidance for the design of TADF and RTP dual emission molecules via internal and external heavy-atom effects.

Enhancing Spin-Orbit Coupling in an Indolocarbazole Multiresonance Emitter by a Sulfur-Containing Peripheral Substituent for a Fast Reverse Intersystem Crossing.

A fast reverse intersystem crossing (RISC) remains an ongoing pursuit for multiresonance (MR) emitters but faces formidable challenges, particularly for indolocarbazole (ICz) derived ones. Here, heavy-atom effect is introduced first to construct ICz-MR emitter using a sulfur-containing substitute, simultaneously enhancing both spin-orbit and spin-vibronic coupling to afford a fast RISC with a rate of 1.2×105s-1, nearly one order of magnitude higher than previous maximum values. The emitter also exhibits an extremely narrow deep-blue emission peaking at 456nm with full-width at half-maxima of merely 12nm and a photoluminescence quantum yield of 92%. Benefiting from its efficient triplet upconversion capability, this emitter achieves not only a high maximum external quantum efficiency (EQE) of 31.1% in organic light-emitting diodes but also greatly alleviates efficiency roll-off, affording record-high EQEs of 29.9% at 1000cdm-2 and 18.7% at 5000cdm-2 among devices with ICz-MR emitters.

Near–Infrared Heptamethine Cyanine Photosensitizers with Efficient Singlet Oxygen Generation for Anticancer Photodynamic Therapy

AbstractNear‐infrared photosensitizers are valuable tools to improve treatment depth in photodynamic therapy (PDT). However, their low singlet oxygen (1O2) generation ability, indicated by low 1O2 quantum yield, presents a formidable challenge for PDT. To overcome this challenge, the heptamethine cyanine was decorated with biocompatible S (Scy7) and Se (Secy7) atom. We observe that Secy7 exhibits a redshift in the main absorption to ~840 nm and an ultra‐efficient 1O2 generation capacity. The emergence of a strong intramolecular charge transfer effect between the Se atom and polymethine chain considerably narrows the energy gap (0.51 eV), and the heavy atom effect of Se strengthens spin–orbit coupling (1.44 cm−1), both of which greatly improved the high triplet state yield (61 %), a state that determines the energy transfer to O2. Therefore, Secy7 demonstrated excellent 1O2 generation capacity, which is ~24.5‐fold that of indocyanine green, ~8.2‐fold that of IR780, and ~1.3‐fold that of methylene blue under low‐power‐density 850 nm irradiation (5 mW cm−2). Secy7 exhibits considerable phototoxicity toward cancer cells buried under 12 mm of tissue. Nanoparticles formed by encapsulating Secy7 within amphiphilic polymers and lecithin, demonstrated promising antitumor and anti‐pulmonary metastatic effects, exhibiting remarkable potential for advancing PDT in deep tissues.

Near-Infrared Heptamethine Cyanine Photosensitizers with Efficient Singlet Oxygen Generation for Anticancer Photodynamic Therapy.

Near-infrared photosensitizers are valuable tools to improve treatment depth in photodynamic therapy (PDT). However, their low singlet oxygen (1O2) generation ability, indicated by low 1O2 quantum yield, presents a formidable challenge for PDT. To overcome this challenge, the heptamethine cyanine was decorated with biocompatible S (Scy7) and Se (Secy7) atom. We observe that Secy7 exhibits a redshift in the main absorption to ~840 nm and an ultra-efficient 1O2 generation capacity. The emergence of a strong intramolecular charge transfer effect between the Se atom and polymethine chain considerably narrows the energy gap (0.51 eV), and the heavy atom effect of Se strengthens spin-orbit coupling (1.44 cm-1), both of which greatly improved the high triplet state yield (61%), a state that determines the energy transfer to O2. Therefore, Secy7 demonstrated excellent 1O2 generation capacity, which is ~24.5-fold that of indocyanine green, ~8.2-fold that of IR780, and ~1.3-fold that of methylene blue under low-power-density 850 nm irradiation (5 mW cm-2). Secy7 exhibits considerable phototoxicity toward cancer cells buried under 12 mm of tissue. Nanoparticles formed by encapsulating Secy7 within amphiphilic polymers and lecithin, demonstrated promising antitumor and anti-pulmonary metastatic effects, exhibiting remarkable potential for advancing PDT in deep tissues.

Guest-Mediated Modulation of Photophysical Pathways in a Coronene Bisimide Cyclophane.

The properties and functions of chromophores utilized by nature are strongly affected by the environment formed by the protein structure in the cells surrounding them. This concept is transferred here to host-guest complexes with the encapsulated guests acting as an environmental stimulus. A new cyclophane host based on coronene bisimide is presented that can encapsulate a wide variety of planar guest molecules with binding constants up to (4.29 ± 0.32) × 1010 M-1 in chloroform. Depending on the properties of the chosen guest, the excited state deactivation of the coronene bisimide chromophore can be tuned by the formation of host-guest complexes toward fluorescence, exciplex formation, charge separation, room-temperature phosphorescence (RTP), or thermally activated delayed fluorescence (TADF). The photophysical processes were investigated by UV/vis absorption, emission, and femto- and nanosecond transient absorption spectroscopy. To enhance the TADF, two different strategies were used by employing suitable guests: the reduction of the singlet-triplet gap by exciplex formation and the external heavy atom effect. Altogether, by using supramolecular host-guest complexation, a versatile multimodal chromophore system is achieved with the coronene bisimide cyclophane.

Dual-Mechanism Design Strategy for High-Efficiency and Long-Lived Organic Afterglow Materials.

Organic room-temperature phosphorescence (RTP) and afterglow materials hold great potential for various applications, but there remain inherent trade-offs between the afterglow efficiency and the lifetime. Here, we propose a dual-mechanism design strategy, leveraging the RTP or thermally activated delayed fluorescence (TADF) mechanism for a high afterglow efficiency and the organic long-persistent luminescence (OLPL) mechanism for a prolonged afterglow duration. The intramolecular charge transfer (ICT)-type difluoroboron β-diketonate molecules with a large S1 dipole moment are doped as the luminescent component into the organic matrix with a large dipole moment, and a series of TADF-type afterglow materials can be achieved with an afterglow efficiency of up to 88.7% and an afterglow lifetime of 200 ms. To prolong the afterglow duration, an electron donor is introduced as the third component to generate traps and facilitate charge separation. The obtained materials exhibit a dual afterglow mechanism, first exhibiting a TADF/RTP afterglow with an afterglow efficiency of up to 50.9%, followed by an hours-long OLPL afterglow emission with an afterglow efficiency of up to 13.1%. Further investigations reveal that an appropriate heavy-atom effect can facilitate the intersystem crossing process, which can promote the charge separation process and thus improve the OLPL afterglow performance. Additionally, rare-earth upconversion materials are introduced into OLPL materials to enable their near-infrared excitation properties, showcasing their potential applications in bioimaging.

Investigation of heavy atom effects and pH sensitivity on the photocatalytic cross-dehydrogenative coupling reaction of halogenated fluorescein dyes

Fluorescein halogenated dyes are excellent photocatalysts for cross-dehydrogenation-coupled (CDC) reaction. In this paper, seven different halo-fluorescein dyes were selected to investigate the influence of heavy halogen atoms and proton concentrations on halo-fluoresceins for photocatalytic CDC reaction. The results showed that the heavy atoms directly affected intersystem crossing (ISC), which could act as a gatekeeper in the photoredox cycle and also affect photoinduced electron transfer (PET) process. Thus, the photocatalytic performance clearly increased in the following order: fluorescein FL (0.11 mol L−1•h−1)＜dibromo-fluorescein FL-2Br (0.19 mol L−1•h−1)＜diiodo-fluorescein FL-2I (0.29 mol L−1•h−1)＜tetrabromo-fluorescein FL-4Br (0.375 mol L−1•h−1)＜tetrabromo-tetrachloro-fluorescein FL-4Br–4Cl (0.53 mol L−1•h−1)＜tetraiodo-fluorescein FL-4I (0.58 mol L−1•h−1)＜ tetraiodo-tetrachloro-fluorescein FL-4I–4Cl (0.74 mol L−1•h−1). Furthermore, the visible light absorption of halogenated fluorescein dyes varied significantly with pH, thereby affecting their photocatalytic activity of CDC reaction. The dianionic FL-4I–4Cl could fully absorb light energy and exhibit excellent photocatalytic performance under mildly alkaline conditions (pH = 8), achieving a CDC reaction conversion rate of 99.92 %, which was 2.6 times higher than that of the lactone form of FL-4I–4Cl under acidic conditions (pH = 2).

Highly Efficient, Low-Roll-Off, Red, "Hot Exciton" Organic Light-Emitting Diodes Promoted by the Heavy-Atom Effect of Selenium.

It is important to attain red hot exciton materials applicable in highly efficient organic light-emitting diodes with low-efficiency roll-off, but their development is restricted by the energy gap law. Herein, the sulfur atom was replaced by a heavier selenium atom based on benzothiadiazole to obtain a new benzoselenadiazole acceptor with a heavy atom effect and stronger electron-withdrawing ability. Two novel red hot exciton materials named BSe-DtBuTPA and BSe-2PhCz-d24 were designed and synthesized based on the benzoselenadiazole unit. Benefiting from the heavy-atom effect of selenium and the small ΔES1T2, both emitters exhibited ultrafast high-lying reverse intersystem crossing rate constants (7.00 × 107 and 1.17 × 107 s-1). The devices based on BSe-DtBuTPA and BSe-2PhCz-d24 demonstrated maximum external quantum efficiencies of 4.81 and 7.15% with emission peaks at 653 and 596 nm, respectively. The device based on deep-red BSe-DtBuTPA exhibited negligible efficiency roll-off of 18.5% at 10000 cd/m2.

Harnessing Solar Power for Oxidation of Organic Compounds by Re(I)Dipyrrinato Complexes.

Metal dipyrrinato complexes of 4d and 5d metals have distinctive features such as high absorption coefficients in the visible section and room temperature phosphorescence in the red region. This work demonstrates the light-assisted oxidation of organic compounds employing rhenium(I)dipyrrinato complexes as catalysts. The heavy atom effect in rhenium(I)dipyrrinato complexes leads to the formation of long-lived triplet excited states, and these complexes can generate singlet oxygen in excellent yields (up to 84 %). A method was developed for photocatalytic aerobic oxidation of sulfides and amines using only 0.05 mol % and 0.025 mol % of the rhenium(I)dipyrrinato complexes, respectively. The method is efficient, and within 2 h, a variety of substrates were oxidized to produce sulfoxides and imines in high yields (up to 97 %). Rhenium(I)dipyrrinato complexes work very well both in visible light and sunlight, making them promising candidates for photocatalytic applications.

High-Performance NIR-II Fluorescent Type I/II Photosensitizer Enabling Augmented Mild Photothermal Therapy of Tumors by Disrupting Heat Shock Proteins.

NIR-II fluorescent photosensitizers as phototheranostic agents hold considerable promise in the application of mild photothermal therapy (MPTT) for tumors, as the reactive oxygen species generated during photodynamic therapy can effectively disrupt heat shock proteins. Nevertheless, the exclusive utilization of these photosensitizers to significantly augment the MPTT efficacy has rarely been substantiated, primarily due to their insufficient photodynamic performance. Herein, the utilization of high-performance NIR-II fluorescent type I/II photosensitizer (AS21:4) is presented as a simple but effective nanoplatform derived from molecule AS2 to enhance the MPTT efficacy of tumors without any additional therapeutic components. By taking advantage of heavy atom effect, AS21:4 as a type I/II photosensitizer demonstrates superior efficacy in producing 1O2 (1O2 quantum yield = 12.4%) and O2 •- among currently available NIR-II fluorescent photosensitizers with absorption exceeding 800nm. In vitro and in vivo findings demonstrate that the 1O2 and O2 •- generated from AS21:4 induce a substantial reduction in the expression of HSP90, thereby improving the MPTT efficacy. The remarkable phototheranostic performance, substantial tumor accumulation, and prolonged tumor retention of AS21:4, establish it as a simple but superior phototheranostic agent for NIR-II fluorescence imaging-guided MPTT of tumors.

One-Pot In Situ Construction of a Highly Stable Acylhydrazone-Derived Dy9 Cluster with Photodynamic Sterilization Property.

The extremely low stability of lanthanide clusters with precise structures and nanometer dimensions in aqueous solutions limits their application in the field of photodynamic sterilization. In this study, an hourglass-shaped nine-nucleated Dy9 cluster (1) with excellent light-driven reactive oxygen species (ROS) generation ability and photodynamic sterilization property was constructed using acylhydrazone multidentate chelating ligands obtained via an in situ reaction. The eight chelating ligands were distributed outside cluster 1, tightly wrapping the cluster core, thus preventing solvent molecules from attacking the cluster nucleus and ensuring the stability of cluster 1 in solution, which was demonstrated via X-ray diffraction and high-resolution electrospray ionization mass spectrometry (HRESI-MS). Time-dependent HRESI-MS monitoring of the self-assembly process of cluster 1 allowed two possible self-assembly mechanisms. The heavy atom effect of multiple Dy(III) ions in the Dy9 cluster enhanced the ISC pathway through spin-orbit coupling, promoting energy transfer from the excited singlet state (S1) to the triplet state (T1), which was stabilized, inducing the generation of more ROS. Cluster 1 showed a remarkable sterilization effect due to the generation of abundant ROS under light irradiation conditions. To our knowledge, this is a rare instance of lanthanide clusters with photodynamic sterilization, providing new horizons for the construction of fast and efficient sterilizers.

Efficient Narrowband Multiple Resonance Thermally Activated Delayed Fluorescent Emitters with Alleviated Efficiency Roll-Off via Steric Shielding and Heavy Atom Effect

Efficient Narrowband Multiple Resonance Thermally Activated Delayed Fluorescent Emitters with Alleviated Efficiency Roll-Off via Steric Shielding and Heavy Atom Effect

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules.

The efficiency of thermally activated delayed fluorescence (TADF) in organic materials relies on rapid intersystem crossing rates and fast conversion of triplet (T) excitons into a singlet (S) state. Heavy atoms such as sulfur or selenium are now frequently incorporated into TADF molecular structures to enhance these properties by increased spin-orbit coupling [spin orbit coupling (SOC)] between the T and S states. Here a series of donor-acceptor (D-A) molecules based on 12H-benzo[4,5]thieno[2,3-a]carbazole and dicyanopyridine is compared with their nonsulfur control molecules designed to probe such SOC effects. We reveal that unexpected intermolecular interactions of the D-A molecules with carbazole-containing host materials instead serve as the dominant pathway for triplet decay kinetics in these materials. In-depth photophysical and computational studies combined with organic light emitting diode measurements demonstrate that the anticipated heavy-atom effect from sulfur is overshadowed by exciplex formation. Indeed, even the unsubstituted acceptor fragments exhibit pronounced TADF exciplex emission in appropriate carbazole hosts. The intermolecular charge transfer and TADF in these systems are further confirmed by detailed time-dependent density functional theory studies. This work demonstrates that anticipated heavy-atom effects in TADF emitters do not always control or even impact the photophysical and electroluminescence properties.

Dual Emission with Efficient Phosphorescence Promoted by Intermolecular Halogen Interactions in Luminescent Tetranuclear Zinc(II) Clusters.

The development of Zn-based phosphorescent materials, associated with a ligand-centered (LC) transition, is extremely limited. Herein, we demonstrated dual emissions including fluorescence and phosphorescence in luminescent tetranuclear Zn(II) clusters [Zn4LI4(μ3-OMe)2X2] (HLI = methyl-5-iode-3-methoxysalicylate; X = I, Br, Cl), incorporating iodine-substituted ligands. Single-crystal X-ray structural analyses and variable-temperature emission spectra studies revealed the presence of iodine substitutions, and intermolecular halogen interactions produced the internal/external heavy-atom effects and yielded strong green phosphorescence with a long emission lifetime (λmax = 510-522 nm, Φem = 0.28-0.47, τav = 0.78-0.95 ms, at 77 K). This work provided a new example that the introduction of halogen interactions is an advantageous approach for inducing phosphorescence in fluorescent metal complexes.