Tertiary phosphine oxides are ubiquitous motifs with essential roles across synthetic chemisty and life sciences, yet the C(sp³)–P coupling remaining less explored. Herein, we report an accessible di-oxo-titanium trichloride complex, operating in combination with Mn powder, that enables a deoxygenative C(sp3)-P coupling of ketones with secondary phosphine oxides. The transformation proceeds under mild conditions and shows good compatibility with carbonyl substrates, including cyclic and acyclic ketones, as well as aliphatic aldehydes. Functionalities, such as carboxyl, acetal, alkyne, sulfonate, phenol, and alcohol are well tolerated.
{"title":"Deoxygenative Phosphonation of Ketones by Titanium","authors":"Yuquan Wang, Kai Yin, Xiaobo Pang, Xing-Zhong Shu","doi":"10.1039/d5sc09520d","DOIUrl":"https://doi.org/10.1039/d5sc09520d","url":null,"abstract":"Tertiary phosphine oxides are ubiquitous motifs with essential roles across synthetic chemisty and life sciences, yet the C(sp³)–P coupling remaining less explored. Herein, we report an accessible di-oxo-titanium trichloride complex, operating in combination with Mn powder, that enables a deoxygenative C(sp3)-P coupling of ketones with secondary phosphine oxides. The transformation proceeds under mild conditions and shows good compatibility with carbonyl substrates, including cyclic and acyclic ketones, as well as aliphatic aldehydes. Functionalities, such as carboxyl, acetal, alkyne, sulfonate, phenol, and alcohol are well tolerated.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"314 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High-performance circularly polarized organic light-emitting diodes (CP-OLEDs) that can simultaneously achieve narrowband emission and high electroluminescence asymmetry factor (gEL) values remain a formidable challenge. In this study, a simple strategy utilizing co-assembled chiral exciplex as host material was employed to fabricate high-performance CP-OLEDs. The exciplex was constructed from chiral acceptor enantiomers (R/S‑TRZ) and an achiral liquid-crystalline donor (CzTPA). Upon thermal annealing, the resulting co-assembled films exhibited circularly polarized luminescence (CPL) with luminescence asymmetry factor (glum) up to 0.58. Introducing the achiral green multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitter to the exciplex host enabled high-performance circularly polarized electroluminescence (CP-EL). The resulting device exhibited a large gEL value of 0.28, a narrow full width at half-maximum (FWHM) of 33 nm, and negligible efficiency roll-off. This work describes the first case of narrowband CP-OLEDs based on chiral co-assembled exciplex host materials, representing one of the highest gEL values of the reported narrowband emission CP-OLEDs to date. It further establishes a general strategy for fabricating high‑performance CP‑OLEDs with readily available achiral emitters, thereby significantly broadening applications in chiral optoelectronics.
{"title":"Chiral Co-assembled Exciplex Host Achieved Extremely Outstanding Narrowband Circularly Polarized Electroluminescence","authors":"Chao Liu, Jun Zeng, Zhenhao Jiang, Yihan Chen, Junsheng Zhang, Yixiang Cheng","doi":"10.1039/d5sc09684g","DOIUrl":"https://doi.org/10.1039/d5sc09684g","url":null,"abstract":"High-performance circularly polarized organic light-emitting diodes (CP-OLEDs) that can simultaneously achieve narrowband emission and high electroluminescence asymmetry factor (gEL) values remain a formidable challenge. In this study, a simple strategy utilizing co-assembled chiral exciplex as host material was employed to fabricate high-performance CP-OLEDs. The exciplex was constructed from chiral acceptor enantiomers (R/S‑TRZ) and an achiral liquid-crystalline donor (CzTPA). Upon thermal annealing, the resulting co-assembled films exhibited circularly polarized luminescence (CPL) with luminescence asymmetry factor (glum) up to 0.58. Introducing the achiral green multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitter to the exciplex host enabled high-performance circularly polarized electroluminescence (CP-EL). The resulting device exhibited a large gEL value of 0.28, a narrow full width at half-maximum (FWHM) of 33 nm, and negligible efficiency roll-off. This work describes the first case of narrowband CP-OLEDs based on chiral co-assembled exciplex host materials, representing one of the highest gEL values of the reported narrowband emission CP-OLEDs to date. It further establishes a general strategy for fabricating high‑performance CP‑OLEDs with readily available achiral emitters, thereby significantly broadening applications in chiral optoelectronics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Athanasios Koutsianos, Erik Svensson Grape, Roman Pallach, Julian Keupp, Rochus Schmid, Andrew Ken Inge, Sebastian Henke
Owing to their dynamic phase behaviour and unique gas sorption properties, flexible metal-organic frameworks (MOFs) have emerged as a promising class of materials for applications in gas-related technologies and beyond. Resolving the crystal structures of the distinct phases is essential for understanding their transformation mechanisms and rational tuning framework responsiveness. Here, we revisit the prototypical flexible MOFs ZIF-7 (Zn(bim)2, bim– = benzimidazolate) and ZIF-9 (Co(bim)2) and resolve the long-standing ambiguity surrounding their guest-free narrow-pore (np) phases. Using microcrystal three-dimensional electron diffraction combined with powder X-ray diffraction (PXRD) and density functional theory calculations, we determine the crystal structures of both np phases. The results rectify previous structural models and incomplete structural descriptions of the np phase of ZIF-7 and, for the first time, establish the structure of the np phase of ZIF-9. In contrast to the high-symmetry, guest-accommodating large-pore (lp) phases adopt distorted, densely packed frameworks with strongly deformed sodalite cages, reduced void fractions, and enhanced framework densities. Variable-temperature PXRD and differential scanning calorimetry further reveal metal-dependent anisotropic thermal expansion of the np phases and entropy-driven np-lp transitions.
{"title":"Deciphering the guest-free crystal structures and thermal breathing of the flexible metal-organic frameworks ZIF-7 and ZIF-9","authors":"Athanasios Koutsianos, Erik Svensson Grape, Roman Pallach, Julian Keupp, Rochus Schmid, Andrew Ken Inge, Sebastian Henke","doi":"10.1039/d5sc08614k","DOIUrl":"https://doi.org/10.1039/d5sc08614k","url":null,"abstract":"Owing to their dynamic phase behaviour and unique gas sorption properties, flexible metal-organic frameworks (MOFs) have emerged as a promising class of materials for applications in gas-related technologies and beyond. Resolving the crystal structures of the distinct phases is essential for understanding their transformation mechanisms and rational tuning framework responsiveness. Here, we revisit the prototypical flexible MOFs ZIF-7 (Zn(bim)<small><sub>2</sub></small>, bim<small><sup>–</sup></small> = benzimidazolate) and ZIF-9 (Co(bim)<small><sub>2</sub></small>) and resolve the long-standing ambiguity surrounding their guest-free narrow-pore (<strong><em>np</em></strong>) phases. Using microcrystal three-dimensional electron diffraction combined with powder X-ray diffraction (PXRD) and density functional theory calculations, we determine the crystal structures of both <strong><em>np</em></strong> phases. The results rectify previous structural models and incomplete structural descriptions of the <strong><em>np</em></strong> phase of ZIF-7 and, for the first time, establish the structure of the <strong><em>np</em></strong> phase of ZIF-9. In contrast to the high-symmetry, guest-accommodating large-pore (<strong><em>lp</em></strong>) phases adopt distorted, densely packed frameworks with strongly deformed sodalite cages, reduced void fractions, and enhanced framework densities. Variable-temperature PXRD and differential scanning calorimetry further reveal metal-dependent anisotropic thermal expansion of the <strong><em>np</em></strong> phases and entropy-driven <strong><em>np</em></strong>-<strong><em>lp</em></strong> transitions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"44 19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138803","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Deli Li, Simin Jiang, Qingchao Liu, Ruizhe Xu, Guo-Xi Yang, wei Li, Shi-Jian Su, Xuchuan Jiang
Benzothienocarbazole (BTC) regioisomers, featuring a relatively heavy sulfur atom, a rigid molecular structure, and moderate electron-donating ability, are used in the design of TADF emitters. Here, a comprehensive structural and optoelectronic investigation of two narrowband blue MR-TADF emitters with rigid donor units is presented. A tertbutyldiphenylamine group at the para position of the boron atom gives these molecules a hybrid frontier molecular orbital distribution, showing both short-range charge transfer (SRCT) and long-range charge transfer (LRCT) traits. The rigid donor units not only diminish the high-frequency vibronic coupling strength of the commonly involved stretching modes but also lower the non-radiative decay rate constants of the triplet state. Consequently, these two emitters produce narrowband blue emissions with full width at half maximum (FWHM) values below 23 nm and high photoluminescence quantum yields over 90%. Non-sensitized OLEDs based on BTC-BN and BFC-BN exhibit blue emissions centered at 476 and 478 nm, with FWHMs of 31 and 29 nm, respectively, and maximum EQEs of 30.9% and 27.7%, respectively. This highlights the unique advantages and importance of the rigid donor in controlling the excited state and enhancing device performance.
{"title":"Rigid Donor Units Strategy Enable Highly Efficient Narrowband Blue Multi-Resonance Thermally Activated Delayed Fluorescence Emitters","authors":"Deli Li, Simin Jiang, Qingchao Liu, Ruizhe Xu, Guo-Xi Yang, wei Li, Shi-Jian Su, Xuchuan Jiang","doi":"10.1039/d5sc10091g","DOIUrl":"https://doi.org/10.1039/d5sc10091g","url":null,"abstract":"Benzothienocarbazole (BTC) regioisomers, featuring a relatively heavy sulfur atom, a rigid molecular structure, and moderate electron-donating ability, are used in the design of TADF emitters. Here, a comprehensive structural and optoelectronic investigation of two narrowband blue MR-TADF emitters with rigid donor units is presented. A tertbutyldiphenylamine group at the para position of the boron atom gives these molecules a hybrid frontier molecular orbital distribution, showing both short-range charge transfer (SRCT) and long-range charge transfer (LRCT) traits. The rigid donor units not only diminish the high-frequency vibronic coupling strength of the commonly involved stretching modes but also lower the non-radiative decay rate constants of the triplet state. Consequently, these two emitters produce narrowband blue emissions with full width at half maximum (FWHM) values below 23 nm and high photoluminescence quantum yields over 90%. Non-sensitized OLEDs based on BTC-BN and BFC-BN exhibit blue emissions centered at 476 and 478 nm, with FWHMs of 31 and 29 nm, respectively, and maximum EQEs of 30.9% and 27.7%, respectively. This highlights the unique advantages and importance of the rigid donor in controlling the excited state and enhancing device performance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"284 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138755","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Quantum chemical calculations using ab initio methods and density functional theory have been carried out on the equilibrium structures and the vibrational spectra of the (valence) isoelectronic compounds N2L2 (L = N2, CO, CS, NO+, CN-). The molecules have a trans-periplanar arrangement of the L2 ligands at the N2 unit. The complexes with L = N2, CO, NO+, CN- are predicted as thermodynamically unstable for dissociation into N2 + 2L with ΔG298 value lying in between -257 kcal/mol (L = NO+) and -73 kcal/mol (L = CO), but the adduct N2(CS)2 is calculated as slightly stable with ΔG298 = 4 kcal/mol. The homolytic dissociation reaction into two fragments N2L2 → 2 NL is energetically less favorable than the heterolytic fragmentation N2L2 → N2 + 2 L, which proceeds synchronously but asymmetrically. The activation barriers for the fragmentation reaction N2L2 → N2 + 2L have values between ΔG≠(298K) = 17 kcal/mol for L = N2 and ΔG≠(298K) = 84 kcal/mol for L = CS. The calculated vibrational frequencies suggest that the molecules N2L2 can be identified by an IR active antisymmetric stretch νas of the ligands L, which is blue shifted for L = CO (Δ = 55 cm-1) and L = NO+ (Δ = 118 cm-1) but it is red shifted for L = CS (Δ = -54 cm-1) and L = CN- (Δ = -133 cm-1) relative to the νas mode of L = N2. The analysis of the bonding situation reveals that there is a total charge donation L→(1Г-N2)←L in all complexes, ranging between 1.38 e (L = CN-) and 0.56 e (L = N2), except in the dication with L = NO+, where a small backdonation in reverse direction L←(1Г-N2)→L with 0.10 e is calculated. EDA-NOCV calculations of N6 show that the best description of the bonding situation is given in terms of dative interactions N2→(1Г-N2)←N2 between central N2 in the excited (1)1Γg singlet state and the terminal N2 fragments in the 1Σg+ electronic ground state.
{"title":"Dinitrogen Complexes N2L2 (L = N2, CO, CS, NO+, CN-)","authors":"Yahui Li, Chengxiang Ding, Lianbin Xie, Sudip Pan, Gernot Frenking","doi":"10.1039/d5sc08399k","DOIUrl":"https://doi.org/10.1039/d5sc08399k","url":null,"abstract":"Quantum chemical calculations using ab initio methods and density functional theory have been carried out on the equilibrium structures and the vibrational spectra of the (valence) isoelectronic compounds N2L2 (L = N2, CO, CS, NO+, CN-). The molecules have a trans-periplanar arrangement of the L2 ligands at the N2 unit. The complexes with L = N2, CO, NO+, CN- are predicted as thermodynamically unstable for dissociation into N2 + 2L with ΔG298 value lying in between -257 kcal/mol (L = NO+) and -73 kcal/mol (L = CO), but the adduct N2(CS)2 is calculated as slightly stable with ΔG298 = 4 kcal/mol. The homolytic dissociation reaction into two fragments N2L2 → 2 NL is energetically less favorable than the heterolytic fragmentation N2L2 → N2 + 2 L, which proceeds synchronously but asymmetrically. The activation barriers for the fragmentation reaction N2L2 → N2 + 2L have values between ΔG≠(298K) = 17 kcal/mol for L = N2 and ΔG≠(298K) = 84 kcal/mol for L = CS. The calculated vibrational frequencies suggest that the molecules N2L2 can be identified by an IR active antisymmetric stretch νas of the ligands L, which is blue shifted for L = CO (Δ = 55 cm-1) and L = NO+ (Δ = 118 cm-1) but it is red shifted for L = CS (Δ = -54 cm-1) and L = CN- (Δ = -133 cm-1) relative to the νas mode of L = N2. The analysis of the bonding situation reveals that there is a total charge donation L→(1Г-N2)←L in all complexes, ranging between 1.38 e (L = CN-) and 0.56 e (L = N2), except in the dication with L = NO+, where a small backdonation in reverse direction L←(1Г-N2)→L with 0.10 e is calculated. EDA-NOCV calculations of N6 show that the best description of the bonding situation is given in terms of dative interactions N2→(1Г-N2)←N2 between central N2 in the excited (1)1Γg singlet state and the terminal N2 fragments in the 1Σg+ electronic ground state.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xuerui Yang, Yuqi Zhou, Junkun Zhou, Xuan Huang, Xin Ao, Guangni Ding, Xiaowei Huang, Naigen Zhou, Guanglei Cui, Yong Yang
The practical development of rechargeable magnesium batteries is fundamentally limited by anode passivation, electrolyte-induced corrosion, and sluggish interfacial Mg2+ transport. Herein, we develop a universal electrolyte design strategy that exploits the synergy between halides and phosphate esters to address these long-standing challenges. Typically, the incorporation of SiBr4 and tris(trimethylsilyl) phosphate (TMSP) extends the electrochemical stability window of the electrolyte from 2.75 to 3.94 V and reconstructs the solvation environment toward bis(trifluoromethanesulfonyl)imide (TFSI-) and TMSP-dominated coordination, significantly lowering the Mg2+ desolvation barrier. Preferential reduction of SiBr4 and TMSP yields a cross-linked, inorganic-rich interphase comprising Mg3(PO4)2, MgSiO3, and MgBr2, which enables fast Mg2+ transport and effectively suppresses parasitic reactions. Meanwhile, Mg3(PO4)2 and MgSiO3 within the interphase serve as robust scaffolds that immobilize soluble MgBr2, further reinforcing interfacial stability. Besides, the electron-rich P=O groups in TMSP further stabilize reactive SiBr3+ intermediates, thereby preventing electrolyte acidification and corrosion. Consequently, MgǁMg symmetric cells cycle stably for 1800 h with a low 0.14 V overpotential. MgǁMo cells reach a peak Coulombic efficiency of 99.97% at 3.4 V after the activation process. Full cells with Mo6S8 cathode deliver a capacity of 80 mAh g-1 with only 0.08% fading over 500 cycles, and Mgǁpolyaniline-intercalated V2O5 (PANI-V2O5) cells achieve 160 mAh g-1 at a cut-off voltage of 2.6 V. This synergistic regulation concept is generalizable to other halides and phosphate esters, providing new mechanistic insights and a general framework for designing stable electrolytes for multivalent batteries.
{"title":"Synergistic Halide and Phosphate Ester Electrolytes for Overcoming Corrosion and Interfacial Challenges in Magnesium Batteries","authors":"Xuerui Yang, Yuqi Zhou, Junkun Zhou, Xuan Huang, Xin Ao, Guangni Ding, Xiaowei Huang, Naigen Zhou, Guanglei Cui, Yong Yang","doi":"10.1039/d6sc00095a","DOIUrl":"https://doi.org/10.1039/d6sc00095a","url":null,"abstract":"The practical development of rechargeable magnesium batteries is fundamentally limited by anode passivation, electrolyte-induced corrosion, and sluggish interfacial Mg2+ transport. Herein, we develop a universal electrolyte design strategy that exploits the synergy between halides and phosphate esters to address these long-standing challenges. Typically, the incorporation of SiBr4 and tris(trimethylsilyl) phosphate (TMSP) extends the electrochemical stability window of the electrolyte from 2.75 to 3.94 V and reconstructs the solvation environment toward bis(trifluoromethanesulfonyl)imide (TFSI-) and TMSP-dominated coordination, significantly lowering the Mg2+ desolvation barrier. Preferential reduction of SiBr4 and TMSP yields a cross-linked, inorganic-rich interphase comprising Mg3(PO4)2, MgSiO3, and MgBr2, which enables fast Mg2+ transport and effectively suppresses parasitic reactions. Meanwhile, Mg3(PO4)2 and MgSiO3 within the interphase serve as robust scaffolds that immobilize soluble MgBr2, further reinforcing interfacial stability. Besides, the electron-rich P=O groups in TMSP further stabilize reactive SiBr3+ intermediates, thereby preventing electrolyte acidification and corrosion. Consequently, MgǁMg symmetric cells cycle stably for 1800 h with a low 0.14 V overpotential. MgǁMo cells reach a peak Coulombic efficiency of 99.97% at 3.4 V after the activation process. Full cells with Mo6S8 cathode deliver a capacity of 80 mAh g-1 with only 0.08% fading over 500 cycles, and Mgǁpolyaniline-intercalated V2O5 (PANI-V2O5) cells achieve 160 mAh g-1 at a cut-off voltage of 2.6 V. This synergistic regulation concept is generalizable to other halides and phosphate esters, providing new mechanistic insights and a general framework for designing stable electrolytes for multivalent batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mahendiran Dharmasivam, Sadia Faiz, Busra Kaya, Tharushi P. Wijesinghe, Mediha Suleymanoglu, Mahan Gholam Azad, Vera Richardson, Ameer Fawad Zahoor, Danuta Kalinowski, William Lewis, Paul V. Bernhardt, Rukhsana Anjum, Des R. Richardson
Designing ligands for cancer has traditionally overlooked complex dissociation and transmetalation in enhancing efficacy. Another neglected criterion is the ligands' ability to intercept the labile Fe(II) pool released after transferrin endocytosis and reduction of transferrin-bound Fe(III). Given iron's essential role in cancer proliferation, disrupting metal homeostasis offers a promising therapeutic strategy. Herein, we introduce a new class of Fe(II)-selective ligands and their Ga(III) complexes for cancer therapy, guided by insights into their dissociative dynamics and transmetalation behavior. Unlike prior approaches focused on static metal coordination, this work integrates dissociation and transmetalation as design features, enabling selective interception of intracellular Fe(II) trafficking. Relative to the ligand, Ga(III) complexation led to a pronounced (p < 0.001–0.0001) enhancement in anti-proliferative activity, with up to a 70-fold increase in potency. This result was in contrast to the modest increase in potency (up to 2.4-fold) observed for the Cu(II) or Zn(II) complexes. Mechanistic dissection demonstrated that, unlike the complete dissociation of the Ga(III) complexes, the relative Zn(II) and Cu(II) complexes underwent only partial dissociation. This difference facilitates complete ligand and Ga(III) release from the complex and may account for the superior cytotoxicity of the Ga(III) complexes versus their Zn(II) and Cu(II) counterparts. Furthermore, their potency was linked to Fe(II) ligation rather than Fe(III), despite electronic similarity to Ga(III). This study introduces three underexplored design principles for anti-cancer ligand engineering: (i) dynamic complex dissociation; (ii) selective intracellular transmetalation using NNO-containing ligands; and (iii) interception of labile Fe(II) generated after endosomal Fe(III) reduction.
{"title":"Implementing the design cues of dissociation dynamics and transmetalation in gallium(III) complexes to promote the anti-proliferative activity of ligands targeting intracellular iron(II) trafficking","authors":"Mahendiran Dharmasivam, Sadia Faiz, Busra Kaya, Tharushi P. Wijesinghe, Mediha Suleymanoglu, Mahan Gholam Azad, Vera Richardson, Ameer Fawad Zahoor, Danuta Kalinowski, William Lewis, Paul V. Bernhardt, Rukhsana Anjum, Des R. Richardson","doi":"10.1039/d5sc06084b","DOIUrl":"https://doi.org/10.1039/d5sc06084b","url":null,"abstract":"Designing ligands for cancer has traditionally overlooked complex dissociation and transmetalation in enhancing efficacy. Another neglected criterion is the ligands' ability to intercept the labile Fe(<small>II</small>) pool released after transferrin endocytosis and reduction of transferrin-bound Fe(<small>III</small>). Given iron's essential role in cancer proliferation, disrupting metal homeostasis offers a promising therapeutic strategy. Herein, we introduce a new class of Fe(<small>II</small>)-selective ligands and their Ga(<small>III</small>) complexes for cancer therapy, guided by insights into their dissociative dynamics and transmetalation behavior. Unlike prior approaches focused on static metal coordination, this work integrates dissociation and transmetalation as design features, enabling selective interception of intracellular Fe(<small>II</small>) trafficking. Relative to the ligand, Ga(<small>III</small>) complexation led to a pronounced (<em>p</em> < 0.001–0.0001) enhancement in anti-proliferative activity, with up to a 70-fold increase in potency. This result was in contrast to the modest increase in potency (up to 2.4-fold) observed for the Cu(<small>II</small>) or Zn(<small>II</small>) complexes. Mechanistic dissection demonstrated that, unlike the complete dissociation of the Ga(<small>III</small>) complexes, the relative Zn(<small>II</small>) and Cu(<small>II</small>) complexes underwent only partial dissociation. This difference facilitates complete ligand and Ga(<small>III</small>) release from the complex and may account for the superior cytotoxicity of the Ga(<small>III</small>) complexes <em>versus</em> their Zn(<small>II</small>) and Cu(<small>II</small>) counterparts. Furthermore, their potency was linked to Fe(<small>II</small>) ligation rather than Fe(<small>III</small>), despite electronic similarity to Ga(<small>III</small>). This study introduces three underexplored design principles for anti-cancer ligand engineering: (i) dynamic complex dissociation; (ii) selective intracellular transmetalation using NNO-containing ligands; and (iii) interception of labile Fe(<small>II</small>) generated after endosomal Fe(<small>III</small>) reduction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Perovskite nanocrystals (PNCs) have emerged as a versatile platform for next-generation optoelectronics owing to high photoluminescence quantum yields, tunable bandgaps, and superior charge transport. Yet, the intrinsic disorder of colloidal systems and limitations of scalable processing severely restrict their performance. The structurally ordered PNCs, called herein as OPNCs, has emerged as a promising strategy to overcome the intrinsic limitations of disordered colloidal systems. Controllable self-assembly enables the formation of ordered superlattices, where collective effects such as enhanced carrier mobility, improved photoluminescence, and miniband formation can be realized. In this perspective, we highlight recent advances in solvent engineering, functionalized ligand design, and external-field modulation that provide new levers for achieving structural control. We further discuss how ordered architectures open pathways toward device applications such as pixelated light-emitting devices, low-threshold lasers, and polarization-sensitive photodetectors. By reframing self-assembly as a controllable and designable process, we propose that OPNC superlattices hold transformative potential for stable and high-performance optoelectronic applications.
{"title":"Ordered Perovskite Nanocrystals: a Transformative Platform for Optoelectronic Applications","authors":"Lujun Zhai, Huifeng Li, Tom Wu, Jianyu Yuan","doi":"10.1039/d5sc08666c","DOIUrl":"https://doi.org/10.1039/d5sc08666c","url":null,"abstract":"Perovskite nanocrystals (PNCs) have emerged as a versatile platform for next-generation optoelectronics owing to high photoluminescence quantum yields, tunable bandgaps, and superior charge transport. Yet, the intrinsic disorder of colloidal systems and limitations of scalable processing severely restrict their performance. The structurally ordered PNCs, called herein as OPNCs, has emerged as a promising strategy to overcome the intrinsic limitations of disordered colloidal systems. Controllable self-assembly enables the formation of ordered superlattices, where collective effects such as enhanced carrier mobility, improved photoluminescence, and miniband formation can be realized. In this perspective, we highlight recent advances in solvent engineering, functionalized ligand design, and external-field modulation that provide new levers for achieving structural control. We further discuss how ordered architectures open pathways toward device applications such as pixelated light-emitting devices, low-threshold lasers, and polarization-sensitive photodetectors. By reframing self-assembly as a controllable and designable process, we propose that OPNC superlattices hold transformative potential for stable and high-performance optoelectronic applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"161 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138753","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hengxuan Qi, Huaxin Li, Zujin Zhao, Hao Liu, Lin Wu, Deli Li, jiasen zhang, Ziru Xin, Chao Xia, Ruixiang Peng, Wenjun Wang, wei Li, Ziyi Ge
We implemented a "terminal engineering" strategy to address the challenges of low efficiency and the difficulty of effectively narrowing the emission spectra within the single boron-nitrogen (BN) multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter system. By adding flexible diphenylamino groups and insulating tert-butyl (t-Bu) groups, respectively, into the structurally simple CzBN and the polycyclic aromatic hydrocarbon (PAH)-based Indo-CzBN, two novel proof-of-concept MR-TADF emitters, DPA-CzBN and Indo-tCzBN, were successfully developed. Notably, the incorporation of t-butyl units into polycyclic aromatic hydrocarbon (PAH)-structured indolocarbazole derivatives not only markedly suppresses the vibration relaxation of the excited state, enabling Indo-tCzBN to achieve an exceptionally narrow full width at half maximum (FWHM) of 19 nm and a high photoluminescence quantum yield (PLQY) of up to 97.5%, but also significantly enhances the horizontal dipole orientation factor (Θ//) of Indo-tCzBN to 85.3%, compared to approximately 73.6% for Indo-CzBN.Accordingly, benefiting from the synergistic effect of a high Θ// factor and a high PLQY, both the non-sensitized and sensitized organic light-emitting diodes (OLEDs) based on Indo-tCzBN achieved maximum external quantum efficiencies (EQEmax) of 37.4% and 39.0%, respectively. These values rank among the highest reported for MR-TADF emitters constructed on a single BN molecular architecture.
{"title":"Single-B/N MR-TADF Emitters Enhancing Electroluminescence Efficiency via 'Terminal Engineering' Strategy","authors":"Hengxuan Qi, Huaxin Li, Zujin Zhao, Hao Liu, Lin Wu, Deli Li, jiasen zhang, Ziru Xin, Chao Xia, Ruixiang Peng, Wenjun Wang, wei Li, Ziyi Ge","doi":"10.1039/d5sc10069k","DOIUrl":"https://doi.org/10.1039/d5sc10069k","url":null,"abstract":"We implemented a \"terminal engineering\" strategy to address the challenges of low efficiency and the difficulty of effectively narrowing the emission spectra within the single boron-nitrogen (BN) multi-resonance thermally activated delayed fluorescence (MR-TADF) emitter system. By adding flexible diphenylamino groups and insulating tert-butyl (t-Bu) groups, respectively, into the structurally simple CzBN and the polycyclic aromatic hydrocarbon (PAH)-based Indo-CzBN, two novel proof-of-concept MR-TADF emitters, DPA-CzBN and Indo-tCzBN, were successfully developed. Notably, the incorporation of t-butyl units into polycyclic aromatic hydrocarbon (PAH)-structured indolocarbazole derivatives not only markedly suppresses the vibration relaxation of the excited state, enabling Indo-tCzBN to achieve an exceptionally narrow full width at half maximum (FWHM) of 19 nm and a high photoluminescence quantum yield (PLQY) of up to 97.5%, but also significantly enhances the horizontal dipole orientation factor (Θ//) of Indo-tCzBN to 85.3%, compared to approximately 73.6% for Indo-CzBN.Accordingly, benefiting from the synergistic effect of a high Θ// factor and a high PLQY, both the non-sensitized and sensitized organic light-emitting diodes (OLEDs) based on Indo-tCzBN achieved maximum external quantum efficiencies (EQEmax) of 37.4% and 39.0%, respectively. These values rank among the highest reported for MR-TADF emitters constructed on a single BN molecular architecture.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"387 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138754","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yan Guo, Menglan Luo, Wenbo Zhang, Peidong Liu, Jin Liu, Shudong Huang, Jiancheng Lv, Bowen Ke, Xianggen Liu
Large Language Models (LLMs) have revolutionized machine learning with their few-shot learning and reasoning capabilities, demonstrating impressive results in fields like natural language processing and computer vision. However, when applied to the domains of biology and chemistry, current LLMs face substantial limitations, particularly in capturing the nuanced relationships between molecular structure and pharmacochemical properties. This challenge has constrained the application of few-shot learning for small-molecule generation and optimization in drug discovery. Here, we introduce DrugLLM, a novel LLM tailored specifically for molecular optimization. DrugLLM leverages Functional Group Tokenization (FGT), which effectively tokenizes molecules for LLM learning, achieving over 53% token compression compared to SMILES. Besides, we propose a new pre-training strategy that enables DrugLLM to iteratively predict and modify molecular structures based on a few prior modifications, aligning each modification toward optimizing a specified pharmacological property. In multiple computational experiments, DrugLLM achieved state-of-the-art performance in few-shot molecular generation, surpassing all the mainstream LLMs including GPT-4. Furthermore, by applying DrugLLM to optimize HCN2 inhibitors, two bioactive compounds were obtained and successfully validated through wet-lab experiments. These results highlight the robust potential of DrugLLM in accelerating the optimization of molecules and AI-driven drug discovery.
{"title":"Few-shot molecular property optimization via a domain-specialized large language model","authors":"Yan Guo, Menglan Luo, Wenbo Zhang, Peidong Liu, Jin Liu, Shudong Huang, Jiancheng Lv, Bowen Ke, Xianggen Liu","doi":"10.1039/d5sc08859c","DOIUrl":"https://doi.org/10.1039/d5sc08859c","url":null,"abstract":"Large Language Models (LLMs) have revolutionized machine learning with their few-shot learning and reasoning capabilities, demonstrating impressive results in fields like natural language processing and computer vision. However, when applied to the domains of biology and chemistry, current LLMs face substantial limitations, particularly in capturing the nuanced relationships between molecular structure and pharmacochemical properties. This challenge has constrained the application of few-shot learning for small-molecule generation and optimization in drug discovery. Here, we introduce DrugLLM, a novel LLM tailored specifically for molecular optimization. DrugLLM leverages Functional Group Tokenization (FGT), which effectively tokenizes molecules for LLM learning, achieving over 53% token compression compared to SMILES. Besides, we propose a new pre-training strategy that enables DrugLLM to iteratively predict and modify molecular structures based on a few prior modifications, aligning each modification toward optimizing a specified pharmacological property. In multiple computational experiments, DrugLLM achieved state-of-the-art performance in few-shot molecular generation, surpassing all the mainstream LLMs including GPT-4. Furthermore, by applying DrugLLM to optimize HCN2 inhibitors, two bioactive compounds were obtained and successfully validated through wet-lab experiments. These results highlight the robust potential of DrugLLM in accelerating the optimization of molecules and AI-driven drug discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"176 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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