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2025 Volume 44 Issue 10
2025, 44(10): 100678
doi: 10.1016/j.cjsc.2025.100678
Abstract:
Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Here, the material design concept of functional units has been applied to prepare a zero-dimensional (0D) organic antimony halide (1-BMP)5(SbCl5)2SbCl4 with two luminescent centers from the inorganic units and the organic units, emitting red emission about 670 nm and cyan emission about 508 nm respectively, combined to form white light. Based on the photoluminescence (PL), the time-resolved PL analysis and density functional theory (DFT) calculation, it is shown that the red and cyan emission comes from STEs related to inorganic units [SbCl5]2– and the fluorescence of organic cations 1-BMP+, respectively. This work provides new methods and ideas for the development of low-cost and eco-friendly white emission phosphors for single-component solid-state WLEDs.
Organic metal halides with white-light emissions have shown significant application prospects in the fields of solid-state lighting and displays, but their structural design and synthesis remain a major challenge. Here, the material design concept of functional units has been applied to prepare a zero-dimensional (0D) organic antimony halide (1-BMP)5(SbCl5)2SbCl4 with two luminescent centers from the inorganic units and the organic units, emitting red emission about 670 nm and cyan emission about 508 nm respectively, combined to form white light. Based on the photoluminescence (PL), the time-resolved PL analysis and density functional theory (DFT) calculation, it is shown that the red and cyan emission comes from STEs related to inorganic units [SbCl5]2– and the fluorescence of organic cations 1-BMP+, respectively. This work provides new methods and ideas for the development of low-cost and eco-friendly white emission phosphors for single-component solid-state WLEDs.
A breakthrough approach to hydrogen peroxide synthesis: Defect-enhanced catalysis in SnSe nanosheets
2025, 44(10): 100679
doi: 10.1016/j.cjsc.2025.100679
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2025, 44(10): 100680
doi: 10.1016/j.cjsc.2025.100680
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2025, 44(10): 100681
doi: 10.1016/j.cjsc.2025.100681
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2025, 44(10): 100682
doi: 10.1016/j.cjsc.2025.100682
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2025, 44(10): 100683
doi: 10.1016/j.cjsc.2025.100683
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2025, 44(10): 100695
doi: 10.1016/j.cjsc.2025.100695
Abstract:
Birefringent materials play a crucial role in light polarization, with important applications in fiber-optic communications. However, developing such materials for the solar-blind region and shorter wavelengths remains challenging due to the inherent trade-off between birefringence and bandgap. In this work, we introduce a strategic assembly of cyanuric rings with biuret units—the latter identified for the first time as a birefringence-active motif—resulting in two new compounds: [H5C2N3O2][H3C3N3O3] (1) and [H5C2N3O2][H3C3N3O3]·xH2O (x ≈ 0.43) (2). Through hydrogen bonding-driven structural optimization, compound 2 achieves a 50% increase in birefringence (Δn = 0.403 @ 546 nm) compared to 1, while retaining a short cutoff edge of 208 nm. This advancement demonstrates that hydrogen-bond-guided structural design, combined with novel functional units, can overcome the traditional birefringence-bandgap conflict, opening new possibilities for short-wavelength birefringent materials with strong optical anisotropy.
Birefringent materials play a crucial role in light polarization, with important applications in fiber-optic communications. However, developing such materials for the solar-blind region and shorter wavelengths remains challenging due to the inherent trade-off between birefringence and bandgap. In this work, we introduce a strategic assembly of cyanuric rings with biuret units—the latter identified for the first time as a birefringence-active motif—resulting in two new compounds: [H5C2N3O2][H3C3N3O3] (1) and [H5C2N3O2][H3C3N3O3]·xH2O (x ≈ 0.43) (2). Through hydrogen bonding-driven structural optimization, compound 2 achieves a 50% increase in birefringence (Δn = 0.403 @ 546 nm) compared to 1, while retaining a short cutoff edge of 208 nm. This advancement demonstrates that hydrogen-bond-guided structural design, combined with novel functional units, can overcome the traditional birefringence-bandgap conflict, opening new possibilities for short-wavelength birefringent materials with strong optical anisotropy.
2025, 44(10): 100702
doi: 10.1016/j.cjsc.2025.100702
Abstract:
Crystalline metal cluster-based organic-inorganic hybrid materials have emerged as a significant frontier in materials chemistry due to their unique structural designability and tunable properties. The bifunctional ligand 2-(hydroxymethyl)-2-(4-pyridyl)-1,3-propanediol (H3L), featuring both hard hydroxyl donors on one side and a soft pyridyl group on the other side, enables selective metal coordination via hard-soft acid-base (HSAB) theory and directs hierarchical metal cluster assembly. This review systematically summarizes the recent advances on metal cluster-based materials coordinated by H3L, including their syntheses, crystal structures, and related physicochemical properties.
Crystalline metal cluster-based organic-inorganic hybrid materials have emerged as a significant frontier in materials chemistry due to their unique structural designability and tunable properties. The bifunctional ligand 2-(hydroxymethyl)-2-(4-pyridyl)-1,3-propanediol (H3L), featuring both hard hydroxyl donors on one side and a soft pyridyl group on the other side, enables selective metal coordination via hard-soft acid-base (HSAB) theory and directs hierarchical metal cluster assembly. This review systematically summarizes the recent advances on metal cluster-based materials coordinated by H3L, including their syntheses, crystal structures, and related physicochemical properties.
2025, 44(10): 100704
doi: 10.1016/j.cjsc.2025.100704
Abstract:
Correlation between tunable optical properties and push-pull structural characters has attracted extensive attention in material science and nonlinear optics. Here, several indacenodithiophene (IDT) derivatives denoted as IDT-2NA, NA-IDT-CN, and IDT-2CN with different terminal substituents are investigated comparatively to demonstrate their intrinsic structure-property relationships. Interestingly, the IDT core acts diverse roles as acceptor (A) and donor (D) in the obtained three derivatives. Symmetric IDT-2NA with a D-A-D architecture shows an absorption maximum around 459 nm in THF. Contrary to the symmetric analog IDT-2CN with a reverse A-D-A feature, NA-IDT-CN with a different D-D′-A motif characterizes an obvious solvent polarity effect. Theoretical calculation and electrostatic potential results confirm the terminal substituents with different electronic conjugation play vital roles in affecting the resultant photophysical properties. Utilizing the femtosecond open-aperture Z-scan technique, significant two-photon absorption (2PA) capabilities are obtained ranging from 540 to 900 nm. The 2PA cross section (δ2PA) maximum about 5390 GM of centrosymmetric IDT-2CN exhibits at 600 nm. Distinct excited-state dynamics with the help of femtosecond transition absorption supports the effective intramolecular charge transfer which accounts for enhancing the δ2PA values. Their potential optical power limiting applications based on the 2PA mechanism were further evaluated. The limiting thresholds were found to be 2.79–3.35 mJ/cm2 for the three IDT derivatives with a sequence of IDT-2CN < IDT-2NA < NA-IDT-CN. The distinct structural motifs and effective 2PA capabilities in the current work may provide reliable insights into the push-pull IDT chromophores for advanced nonlinear optical applications.
Correlation between tunable optical properties and push-pull structural characters has attracted extensive attention in material science and nonlinear optics. Here, several indacenodithiophene (IDT) derivatives denoted as IDT-2NA, NA-IDT-CN, and IDT-2CN with different terminal substituents are investigated comparatively to demonstrate their intrinsic structure-property relationships. Interestingly, the IDT core acts diverse roles as acceptor (A) and donor (D) in the obtained three derivatives. Symmetric IDT-2NA with a D-A-D architecture shows an absorption maximum around 459 nm in THF. Contrary to the symmetric analog IDT-2CN with a reverse A-D-A feature, NA-IDT-CN with a different D-D′-A motif characterizes an obvious solvent polarity effect. Theoretical calculation and electrostatic potential results confirm the terminal substituents with different electronic conjugation play vital roles in affecting the resultant photophysical properties. Utilizing the femtosecond open-aperture Z-scan technique, significant two-photon absorption (2PA) capabilities are obtained ranging from 540 to 900 nm. The 2PA cross section (δ2PA) maximum about 5390 GM of centrosymmetric IDT-2CN exhibits at 600 nm. Distinct excited-state dynamics with the help of femtosecond transition absorption supports the effective intramolecular charge transfer which accounts for enhancing the δ2PA values. Their potential optical power limiting applications based on the 2PA mechanism were further evaluated. The limiting thresholds were found to be 2.79–3.35 mJ/cm2 for the three IDT derivatives with a sequence of IDT-2CN < IDT-2NA < NA-IDT-CN. The distinct structural motifs and effective 2PA capabilities in the current work may provide reliable insights into the push-pull IDT chromophores for advanced nonlinear optical applications.
2025, 44(10): 100705
doi: 10.1016/j.cjsc.2025.100705
Abstract:
The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists. Nevertheless, the achievement on photothermal property enhancement and their application in solar-driven water evaporation via structural modulation remain scarce. Here, four organometallic cages 1, 2, 3 and 4 with different functional sites are synthesized via reasonably selecting different building units E1, E2, E3 and E4 based on a tetradentate pyridyl ligand L1. These complexes are characterized by single-crystal X-ray diffraction analysis, nuclear magnetic resonance (NMR) spectroscopy and ESI-TOF-MS analysis. Notably, they exhibit different near-infrared (NIR) photothermal conversion properties due to variations in their size, conjugated area, and electron-withdrawing characteristic of halogen atoms in building units. Compound 4 shows the optimal photothermal performance among this series, with notably enhanced near-infrared absorption and the highest photothermal conversion efficiency. The radical effect of the building unit plays an important role in photothermal conversion ability, as evidenced by the significant EPR signal changes. Therefore, compound 4 is used to construct new membrane 1′, achieving a solar power-induced water steam generation rate of 1.92 kg·m-2·h-1, demonstrating its suitability for the collection of fresh water through desalination and wastewater treatment. This research provides a new strategy for synthesizing and optimizing photothermal conversion property of half sandwich organometallic cages.
The structural synthesis and property exploration of organometallic cages have always attracted widespread attention from chemists. Nevertheless, the achievement on photothermal property enhancement and their application in solar-driven water evaporation via structural modulation remain scarce. Here, four organometallic cages 1, 2, 3 and 4 with different functional sites are synthesized via reasonably selecting different building units E1, E2, E3 and E4 based on a tetradentate pyridyl ligand L1. These complexes are characterized by single-crystal X-ray diffraction analysis, nuclear magnetic resonance (NMR) spectroscopy and ESI-TOF-MS analysis. Notably, they exhibit different near-infrared (NIR) photothermal conversion properties due to variations in their size, conjugated area, and electron-withdrawing characteristic of halogen atoms in building units. Compound 4 shows the optimal photothermal performance among this series, with notably enhanced near-infrared absorption and the highest photothermal conversion efficiency. The radical effect of the building unit plays an important role in photothermal conversion ability, as evidenced by the significant EPR signal changes. Therefore, compound 4 is used to construct new membrane 1′, achieving a solar power-induced water steam generation rate of 1.92 kg·m-2·h-1, demonstrating its suitability for the collection of fresh water through desalination and wastewater treatment. This research provides a new strategy for synthesizing and optimizing photothermal conversion property of half sandwich organometallic cages.
2025, 44(10): 100707
doi: 10.1016/j.cjsc.2025.100707
Abstract:
Non-centrosymmetric (NCS) crystalline structures, critical for second harmonic generation (SHG) in all-solid-state lasers, are far less prevalent than their centrosymmetric (CS) counterparts. In this study, we report a structural transformation from CS to NCS configuration in benzenesulfonate derivatives via hydroxyl group incorporation, as illustrated by the transition in the newly discovered CN3H6C6H5SO3 (CS) and CN3H6C6H4SO3(OH) (NCS). The introduced hydroxyl groups induce hydrogen bond reconstruction, effectively breaking the original centrosymmetry. The resulting NCS compound exhibits remarkable nonlinear optical (NLO) properties, including a strong SHG response (1.6 × KDP with the particle sizes of 200–250 μm), a wide bandgap (UV cutoff at 290 nm, corresponding band gap is 4.37 eV), and a large birefringence (0.21@1064 nm), demonstrating excellent potential as an UV NLO crystal material.
Non-centrosymmetric (NCS) crystalline structures, critical for second harmonic generation (SHG) in all-solid-state lasers, are far less prevalent than their centrosymmetric (CS) counterparts. In this study, we report a structural transformation from CS to NCS configuration in benzenesulfonate derivatives via hydroxyl group incorporation, as illustrated by the transition in the newly discovered CN3H6C6H5SO3 (CS) and CN3H6C6H4SO3(OH) (NCS). The introduced hydroxyl groups induce hydrogen bond reconstruction, effectively breaking the original centrosymmetry. The resulting NCS compound exhibits remarkable nonlinear optical (NLO) properties, including a strong SHG response (1.6 × KDP with the particle sizes of 200–250 μm), a wide bandgap (UV cutoff at 290 nm, corresponding band gap is 4.37 eV), and a large birefringence (0.21@1064 nm), demonstrating excellent potential as an UV NLO crystal material.
2025, 44(10): 100710
doi: 10.1016/j.cjsc.2025.100710
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2025, 44(10): 100712
doi: 10.1016/j.cjsc.2025.100712
Abstract:
Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl)phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1–C1–C2–N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units Rh–B1, Rh–B2, Rh–B3, and Rh–B4 featuring Cp∗RhIII (Cp∗ = η5-pentamethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh-3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through programming different combination of noncovalent interactions (π-π stacking, CH⋯π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp∗IrIII analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.
Mechanically interlocked molecules (MIMs) have unique properties with broad applications, yet constructing both knotted and linked topologies from the same ligand remains challenging due to their distinct geometric demands. To address this, we design and synthesize a conformationally adaptive ligand 4,7-bis(3-(pyridin-4-yl)phenyl) benzo[c][1,2,5]thiadiazole (L1) with a tunable torsional angle θ of N1–C1–C2–N2 ranging from 7.5° to 108.9°. Utilizing coordination-driven self-assembly at ambient temperature, L1 selectively assembles with binuclear half-sandwich units Rh–B1, Rh–B2, Rh–B3, and Rh–B4 featuring Cp∗RhIII (Cp∗ = η5-pentamethylcyclopentadienyl) into distinct topologies: Solomon links Rh-1, trefoil knots Rh-2, molecular tweezers Rh-3, and Rh-4, respectively. Crucially, the self-adaptability of ligand L1 directs topology formation through programming different combination of noncovalent interactions (π-π stacking, CH⋯π interaction, and lone pair-π interaction), thus navigating divergent assembly pathways by conformational switching, as evidenced by X-ray crystallography analysis, independent gradient model (IGM) analysis, detailed nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization time-of-flight/mass spectrometry (ESI-TOF/MS). This strategy can also be extended to construct Cp∗IrIII analogs (Solomon links Ir-1, trefoil knots Ir-2, molecular tweezers Ir-3 and Ir-4), demonstrating metal-independent control and achieving intricate topologies in a high yield.
2025, 44(10): 100714
doi: 10.1016/j.cjsc.2025.100714
Abstract:
The donor-acceptor hydrogen bonding strategy has been proposed to enforce coplanar packing of anisotropic π-conjugated units, thereby maximizing the material's achievable birefringence. Herein, employing this strategy, we successfully obtain two highly coplanar birefringent crystals, FAHC2O4 and FAH2C3N3S3 (FA+: CH5N2+, formamidinium). FAHC2O4 shows a wide bandgap (4.20 eV), while FAH2C3N3S3 exhibits a narrower bandgap (2.96 eV) due to the involvement of sulfur atom. Both crystals display notable birefringence in their respective material classes: 0.275@546 nm and 0.504@546 nm, respectively. X-ray crystallography and computational studies attribute the pronounced birefringence to their π-conjugated moieties and their near-coplanar configurations. Comparative analysis of FAHC2O4 and FAH2C3N3S3 further establishes that the hydrogen bond strength directly influences the molecular coplanarity degree. These findings provide new insights for applying the donor-acceptor hydrogen bonding strategy in the rational design of high-performance birefringent materials.
The donor-acceptor hydrogen bonding strategy has been proposed to enforce coplanar packing of anisotropic π-conjugated units, thereby maximizing the material's achievable birefringence. Herein, employing this strategy, we successfully obtain two highly coplanar birefringent crystals, FAHC2O4 and FAH2C3N3S3 (FA+: CH5N2+, formamidinium). FAHC2O4 shows a wide bandgap (4.20 eV), while FAH2C3N3S3 exhibits a narrower bandgap (2.96 eV) due to the involvement of sulfur atom. Both crystals display notable birefringence in their respective material classes: 0.275@546 nm and 0.504@546 nm, respectively. X-ray crystallography and computational studies attribute the pronounced birefringence to their π-conjugated moieties and their near-coplanar configurations. Comparative analysis of FAHC2O4 and FAH2C3N3S3 further establishes that the hydrogen bond strength directly influences the molecular coplanarity degree. These findings provide new insights for applying the donor-acceptor hydrogen bonding strategy in the rational design of high-performance birefringent materials.
2025, 44(10): 100719
doi: 10.1016/j.cjsc.2025.100719
Abstract:
Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medicine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.
Chiral metal-organic frameworks (CMOFs), a class of highly crystalline and porous materials with tailorable chiral characteristics, have currently become an interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medicine, pharmacology, biology, crystal engineering, environmental science, etc. Their special structural features such as porosity, modularity, and chirality have endowed them with a variety of unique effects in promoting enantioselective processes, particularly asymmetric catalysis. Here, we provide a brief review of the state of CMOF field from the privileged ligand design to the heterogeneous enantioselective catalysis. We hope that this review will provide researchers a better understanding of CMOF chemistry and facilitate the future research endeavors for rationally designing privileged chiral framework materials for challenging catalytic applications.
2025, 44(10): 100728
doi: 10.1016/j.cjsc.2025.100728
Abstract:
Photocatalytic CO2 reduction is a promising route toward carbon neutrality, yet its practical application is hindered by the high activation energy barrier of CO2, rapid recombination of photo-generated electrons, and poor product selectivity of traditional catalysts. Frustrated Lewis pairs (FLPs), which feature spatially separated Lewis acid and base sites, have recently emerged as a novel strategy to overcome these limitations. This review systematically examines the progress in FLPs-based photocatalytic systems. We focus on the construction strategies for FLPs active sites, the optimization of charge carrier dynamics, and the synergistic electron transfer mechanisms with photoactive components. Central theme is the elucidation of microscopic mechanisms governing CO2 activation, key intermediate conversion, and the efficient utilization of photogenerated electrons. By synthesizing current knowledge and outlining future prospects, this review aims to provide a theoretical framework that guides the rational design of highly active and selective catalysts for solar-driven CO2 reduction.
Photocatalytic CO2 reduction is a promising route toward carbon neutrality, yet its practical application is hindered by the high activation energy barrier of CO2, rapid recombination of photo-generated electrons, and poor product selectivity of traditional catalysts. Frustrated Lewis pairs (FLPs), which feature spatially separated Lewis acid and base sites, have recently emerged as a novel strategy to overcome these limitations. This review systematically examines the progress in FLPs-based photocatalytic systems. We focus on the construction strategies for FLPs active sites, the optimization of charge carrier dynamics, and the synergistic electron transfer mechanisms with photoactive components. Central theme is the elucidation of microscopic mechanisms governing CO2 activation, key intermediate conversion, and the efficient utilization of photogenerated electrons. By synthesizing current knowledge and outlining future prospects, this review aims to provide a theoretical framework that guides the rational design of highly active and selective catalysts for solar-driven CO2 reduction.
2025, 44(10): 100733
doi: 10.1016/j.cjsc.2025.100733
Abstract:
In this paper, the third-order nonlinear optical (NLO) properties of covalent organic framework (COF) materials with conjugated amphoteric ion structure are studied for the first time. A highly ordered crystalline ultrathin films of the ionic COF material PySQ-iCOF was successfully fabricated using a solid-liquid interface method, meanwhile the building units extracted to be independent small molecule, 1-PySA, were synthesized for comparative studies. Compared to 1-PySA, PySQ-iCOF possesses not only a larger conjugated system but also exhibits enhanced polarization and charge transfer capabilities. The NLO properties of PySQ-iCOF and the small molecule 1-PySA were investigated using Z-scan technique at a wavelength of 532 nm, revealing the PySQ-iCOF thin film exhibits outstanding NLO performance. Specifically, it demonstrates saturable absorption under nanosecond (ns) pulse laser irradiation (β = -9.59 × 10-6 m/W), while exhibiting reverse saturable absorption under femtosecond (fs) pulse conditions (β = 6.91 × 10-8 m/W). Furthermore, the PySQ-iCOF film exhibits strong negative refractive nonlinearity, -6 × 10-12 m2/W for ns and -3.8 × 10-13 m2/W for fs, respectively. Transient absorption spectroscopy studies indicate that the pulse-width-dependent nonlinear absorption characteristics of the PySQ-iCOF film originate from the generation of triplet excited states. Both nonlinear absorption coefficient and nonlinear refractive index of the PySQ-iCOF film surpass those of most reported organic materials measured under comparable conditions, which provides huge potential in all-optical manipulating and switching at the nanoscale as outstanding NLO materials.
In this paper, the third-order nonlinear optical (NLO) properties of covalent organic framework (COF) materials with conjugated amphoteric ion structure are studied for the first time. A highly ordered crystalline ultrathin films of the ionic COF material PySQ-iCOF was successfully fabricated using a solid-liquid interface method, meanwhile the building units extracted to be independent small molecule, 1-PySA, were synthesized for comparative studies. Compared to 1-PySA, PySQ-iCOF possesses not only a larger conjugated system but also exhibits enhanced polarization and charge transfer capabilities. The NLO properties of PySQ-iCOF and the small molecule 1-PySA were investigated using Z-scan technique at a wavelength of 532 nm, revealing the PySQ-iCOF thin film exhibits outstanding NLO performance. Specifically, it demonstrates saturable absorption under nanosecond (ns) pulse laser irradiation (β = -9.59 × 10-6 m/W), while exhibiting reverse saturable absorption under femtosecond (fs) pulse conditions (β = 6.91 × 10-8 m/W). Furthermore, the PySQ-iCOF film exhibits strong negative refractive nonlinearity, -6 × 10-12 m2/W for ns and -3.8 × 10-13 m2/W for fs, respectively. Transient absorption spectroscopy studies indicate that the pulse-width-dependent nonlinear absorption characteristics of the PySQ-iCOF film originate from the generation of triplet excited states. Both nonlinear absorption coefficient and nonlinear refractive index of the PySQ-iCOF film surpass those of most reported organic materials measured under comparable conditions, which provides huge potential in all-optical manipulating and switching at the nanoscale as outstanding NLO materials.
2025, 44(10): 100735
doi: 10.1016/j.cjsc.2025.100735
Abstract:
It remains highly challenging to achieve the high-order nonlinear optical (NLO) properties of atomically precise metal nanoclusters via template-maintained manipulation. Here, based on the M1Ag24(SR)18 (M = Ag/Au/Pt/Pd; SR = 2,4-dimethylthiophenol) cluster template, we demonstrated that the innermost kernel alloying rendered these nanoclusters highly controllable towards the nonlinear optics. The Pd-alloyed Pd1Ag24(SR)18 only displayed single-photon-excited fluorescence, while the homo-silver Ag25(SR)18 nanocluster generated the two-photon-excited fluorescence characterization. The Au- and Pt-doped M1Ag24(SR)18 nanoclusters showed high-order three- and four-photon-excited fluorescence, respectively, demonstrating that the order-by-order control over the nonlinear optics of nanoclusters has been accomplished. Moreover, Pt1Ag24(SR)18 with high-order NLO characterization exhibited the best optical limiting performance under 1000 nm excitation, in agreement with its most prominent NLO property. Overall, this work presents an intriguing cluster template that enables successive order control over the nonlinear optics of atomically precise metal nanoclusters, hopefully paving the way for developing cluster-based nanomaterials with customized optical characterizations.
It remains highly challenging to achieve the high-order nonlinear optical (NLO) properties of atomically precise metal nanoclusters via template-maintained manipulation. Here, based on the M1Ag24(SR)18 (M = Ag/Au/Pt/Pd; SR = 2,4-dimethylthiophenol) cluster template, we demonstrated that the innermost kernel alloying rendered these nanoclusters highly controllable towards the nonlinear optics. The Pd-alloyed Pd1Ag24(SR)18 only displayed single-photon-excited fluorescence, while the homo-silver Ag25(SR)18 nanocluster generated the two-photon-excited fluorescence characterization. The Au- and Pt-doped M1Ag24(SR)18 nanoclusters showed high-order three- and four-photon-excited fluorescence, respectively, demonstrating that the order-by-order control over the nonlinear optics of nanoclusters has been accomplished. Moreover, Pt1Ag24(SR)18 with high-order NLO characterization exhibited the best optical limiting performance under 1000 nm excitation, in agreement with its most prominent NLO property. Overall, this work presents an intriguing cluster template that enables successive order control over the nonlinear optics of atomically precise metal nanoclusters, hopefully paving the way for developing cluster-based nanomaterials with customized optical characterizations.
