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Coordination Polymers Based on Organic–Inorganic Hybrid Rigid Rod Comprising a Backbone of Anderson-Evans POMs
摘要： To construct polyoxometalates coordination polymers (PCPs), we prepared two pyridine ligand functionalized Anderson POMs: (TBA)3[MnMo6O18((OCH2)3CN=CH-4-Py)2]·DMF ((TBA)3POM-1, TBA = tetrabutyl ammonium, Py = pyridine) and (TBA)3[MnMo6O18((OCH2)3CN=CH-3-Py)2] ((TBA)3POM-2) via the post-functionalization of (TBA)3[MnMo6O18((OCH2)3CNH2)2] (Anderson-NH2) by 4-pyridinealdehyde and 3-pyridinealdehyde, respectively. They are characterized using X-ray single crystal diffraction, MALDI-TOF MS, ESI MS, FT-IR, UV-Vis and 1H NMR . The self-assembly of (TBA)3POM-1 and [Cu(PPh3)2(CH3CN)2]ClO4 (CuP2) in the mole ratios of 1 : 2 and 1 : 3, both gave the same 1D double chain with the molecular formula of (NBu4)n{[Cu(PPh3)2]2(POM-1)}n (7.5DMF)n (1). On the contrary, the self-assembly of (TBA)3POM-2 and CuP2 in the mole ratio of 1:2 yields a 2D coordination polymer of (TBA)n{[Cu(PPh3)2]2(POM-2)}n·(2DMF)n (2), while that self-assembly process in the mole ratio of 1:3 results in different 2D coordination polymer of {[Cu(PPh3)2]3(POM-2)·(CH3CN)}n·(5CH3CN)n (3). Compounds 1-3 can keep their skeleton structures below 230oC. They exhibit intense green emission (496nm for 1; 537nm for 2; 530nm for 3) by ultra-violet irradiation (327nm for 1; 303nm for 2; 331nm for 3), which can be tentatively ascribed as ILCT with metal perturbation.
关键词： Luminescence,Polyoxometalates,Pyridine,Coordination Polymer,Copper (I)
更新于2025-09-23 15:23:52
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Photocatalytic oxidative desulfurization and denitrogenation of fuels over sodium doped graphitic carbon nitride nanosheets under visible light irradiation
摘要： A cost-efficient photocatalytic oxidative denitrogenation and desulfurization system for fuels under visible light was developed on the basis of Na doped g-C3N4 nanosheets catalyst. The process adopted molecular O2 as oxidant to substitute for the expensive H2O2, and it adapted to the removal of small molecules of pyridine and thiophene. Na doped g-C3N4 nanosheets were obtained via a simple mixed-calcination pathway using NaCl as Na source. The structural, photophysical and chemical properties of the photocatalysts were characterized and compared to those of the original g-C3N4. It was verified that Na was successfully doped in the g-C3N4 lattice in a uniform chemical state. Moderate amount of Na doped in g-C3N4 generated the highly dispersed and porous nanosheets, which further improved the surface energy and reduce the recombination rate of electron-hole pairs. Na doped g-C3N4 exhibited enhanced performance simultaneously in the photocatalytic oxidative denitrogenation and desulfurization. The optimal catalyst obtained considerable removal efficiency for pyridine and thiophene, depending on its improved structural and photochemical properties by Na doping. A proposed mechanism revealed that the holes acted as the major active species for the denitrogenation and desulfurization, while the superoxide radicals originating from the combination of electron and O2 gave a promotion effect.
关键词： Pyridine,Sodium doping,Graphitic carbon nitride,Thiophene,Photocatalytic oxidation
更新于2025-09-23 15:23:52
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A new lysosome-targetable fluorescent probe with a large Stokes shift for detection of endogenous hydrogen polysulfides in living cells
摘要： Hydrogen polysulfides (H2Sn, n>1) influence a variety of important biological functions and activities associated with hydrogen sulfide (H2S). The development of probes for rapid, selective, and sensitive detection of H2Sn still remains a great challenge. Lysosome plays crucial roles in various physiological processes among living cells, which arouse high interest in detecting endogenous lysosome-targetable H2Sn. To the best of our knowledge, there is no lysosome-targetable probe for H2Sn has been reported. In this work, a new lysosome-targetable probe NIPY-NF, based on the scaffold of imidazo[1,5-α]pyridine, with a large Stokes shift (215 nm), low detection limit (84 nM), fast response time (6 min) and low cytotoxicity was designed and synthesized. Furthermore, NIPY-NF was successfully applied into the cell imaging for detection of endogenous lysosome-targetable H2Sn.
关键词： Hydrogen polysulfides,Fluorescent probe,Lysosome,Cell imaging,Imidazo[1,5-α]pyridine
更新于2025-09-23 15:23:52
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One-dimensional coordination polymers based on a new 3-position substituted imidazo[1,2-a]pyridine ligand: Crystal structures, photoluminescent and magnetic properties
摘要： A new 3-position substituted imidazo[1,2-a]pyridine ligand, namely, 5-(2-chloroimidazo[1,2-a]pyridine-3-carboxamido) isophthalic acid (H2L) was synthesized and characterized by 1H NMR spectroscopy. Based on this ligand, three isostructural one-dimensional coordination polymers, [ML(H2O)2]n (M = Zn (1), Ni (2) and Co (3)) were synthesized under the solvothermal conditions, and structurally characterized by single crystal X-ray diffraction, infrared spectroscopy, powder X-ray diffraction and elemental analyses. The coordination polymer 1 reveals similar photoluminescent spectrum to H2L ligand, but possesses the enhanced phosphorescent emission and higher phosphorescent quantum yield, compared to H2L ligand. Furthermore, the magnetic properties of coordination polymers 2 and 3 have been investigated, the results show there are antiferromagnetic interactions between the NiII ions or CoII ions in 2 or 3.
关键词： Photoluminescence,Coordination polymers,Imidazo[1,2-a]pyridine,X-ray structures,Magnetic properties
更新于2025-09-23 15:22:29
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Synthesis, photophysical properties and DFT studies of the pyridine-imidazole (PyIm) Cu(I) complexes: Impact of the pyridine ring functionalized by different substituents
摘要： A series of the pyridine-imidazole (PyIm) Cu(I) complexes with different substituents (bromide (P1), methyl (P2), and phenyl (P3)) attached on the pyridine ring are synthesized and characterized. All the complexes show the typical metal-to-ligand charge transfer (MLCT) absorption in the visible region. Complex P1 with an electron-withdrawing substituent on the pyridine ring, e.g., a bromine group, shows a red shift of the emission wavelength. Conversely, an electron-donating substituent on the pyridine ring in complex P2, e.g., a methyl group, shifts the emission to longer wavelength. Similarly, complex P3 containing the extended π-conjugation system of the ligand also exhibits a red shift of the emission wavelength. All of the complexes exhibit efficient green-yellow emission in PMMA films at room temperature with emission wavelength of 547–569 nm and quantum yields of 24.8–53.0%. Meanwhile, DFT and TDDFT methods were employed to explain the photophysical properties.
关键词： Pyridine-imidazole,Copper (I) complex,Metal-to-ligand charge transfer,Molar extinction coefficient,Density functional theory
更新于2025-09-23 15:22:29
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Impact of t-butyl group on the singlet-triplet energy gap via weak orbital overlap of [1,2,5]-thiadiazolo[3,4-C]pyridine based TADF emitters: Structural modification
摘要： We theoretically investigated the combination of D-A and D-spacer (phenyl ring) -A with an electron donating alkyl (t-butyl) group. The strategy of twisting the geometry of the molecule with the alkyl substituents exclusion of strong electron withdrawing or donating groups leads to gain efficient deep blue-blue TADF emitter through maintaining the band gap while the reduction of singlet-triplet energy gap (EST). The t-butyl group strongly twisted the conformation of molecules by the steric hindrance resulted in weak HOMO and LUMO overlap (IH/L) and efficient spatial separation of HOMO and LUMO (rH/L) in the S0 state. In contrast, designed molecules S1 state own large HOMO and LUMO overlap of excited singlet state (IS) and inefficient spatial separation of HOMO and LUMO. The computed results indicated that introducing alkyl group into the phenyl ring of the acceptor of the designed molecules cannot affect the ΔEST. The ΔEST is mainly related to the IH/L, which can be adjusted by tuning the orbital IH/L. The large modular orbital overlap at S1 and T1 excited states resulted large ΔEST occurs in the range of 0.38 to 0.59eV whose dominant contribution switches from charge transfer (CT) to local excitation (LE). Our studied results reiterate (10.1038/srep10923) that modular orbital overlap of IS, HOMO and LUMO overlap of excited triplet state IT, spatial separation of HOMO and LUMO in the excited singlet state (rS) and spatial separation of HOMO and LUMO in the excited triplet state (rT) are the essential factors to determine ΔEST when inconsistencies between ΔEST and IH/L. Increasing the dihedral angle between D and A from molecule 1-4 (9-12), decrease the transition dipole moment which lowering the oscillator strength. When changing the connection position between D and A, molecules 5-8, the oscillator strength reduced to half with respect to molecules 1-4 and 9-12. The present work provides a theoretical understanding of the impact of alkyl substituents on the overlap of HOMO-LUMO resulting to tuning the ΔEST, as well as its influence on the oscillator strength may be a reliable idea to design efficient TADF emitters.
关键词： [1,2,5]-thiadiazolo[3,4-C]pyridine,HOMO-LUMO orbital overlap,fluorescence radiative decay rate,TADF,singlet-triplet energy gap
更新于2025-09-23 15:21:01
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Imidazo[1,2-a]pyridine as an electron acceptor to construct?? high-performance deep-blue organic light-emitting diodes with negligible efficiency roll-off
摘要： Two novel bipolar deep-blue fluorescent emitters, IP-PPI and IP-DPPI featuring different lengths of phenyl bridge, were designed and synthesized, in which imidazo[1,2-a]pyridine (IP) and phenanthroimidazole (PI) were proposed as an electron-acceptor and an electron donor respectively. Both of them exhibited outstanding thermal stability and high emission quantum yield. All the devices based on these two materials showed negligible efficiency roll-off with increasing current density. Impressively, non-doped organic light-emitting diodes (OLEDs) based on IP-PPI and IP-DPPI exhibited EQE of 4.85% and 4.74% with CIE coordinates of (0.153, 0.097) and (0.154, 0.114) at 10000 cd m-2, respectively. Besides, the 40 wt% IP-PPI doped device maintained high EQE of 5.23% with CIE coordinates of (0.154, 0.077) at 10000 cd m-2. The doped device based on 20 wt% IP-DPPI exhibited higher deep-blue electroluminescence (EL) performance with maximum EQE up to 6.13% at CIE of (0.153, 0.078) and remained EQE of 5.07% at 10000 cd m-2. To the best of our knowledge, these performances are among the state-of-the art devices with CIEy ≤ 0.08 at a high brightness of 10000 cd m-2. Furthermore, by doping a red phosphorescent dye Ir(MDQ)2 into IP-PPI and IP-DPPI hosts, high-performance red PhOLEDs with EQE of 20.8% and 19.1% were achieved, respectively. This work may provide a new approach for designing highly efficient deep-blue emitters with negligible roll-off for OLED applications.
关键词： negligible efficiency roll-off,imidazo[1,2-a]pyridine,OLEDs,deep-blue
更新于2025-09-23 15:19:57
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Shaping Metallic Nanolattices: Design by Microcontact Printing from Wrinkled Stamps
摘要： A method for the fabrication of well-defined metallic nanostructures is presented here in a simple and straightforward fashion. As an alternative to lithographic techniques, this routine employs microcontact printing utilizing wrinkled stamps, which are prepared from polydimethylsiloxane (PDMS), and includes the formation of hydrophobic stripe patterns on a substrate via the transfer of oligomeric PDMS. Subsequent backfilling of the interspaces between these stripes with a hydroxyl-functional poly(2-vinyl pyridine) then provides the basic pattern for the deposition of citrate-stabilized gold nanoparticles promoted by electrostatic interaction. The resulting metallic nanostripes can be further customized by peeling off particles in a second microcontact printing step, which employs poly(ethylene imine) surface-decorated wrinkled stamps, to form nanolattices. Due to the independent adjustability of the period dimensions of the wrinkled stamps and stamp orientation with respect to the substrate, particle arrays on the (sub)micro-scale with various kinds of geometries are accessible in a straightforward fashion. This work provides an alternative, cost-effective, and scalable surface-patterning technique to fabricate nanolattice structures applicable to multiple types of functional nanoparticles. Being a top-down method, this process could be readily implemented into, e.g., the fabrication of optical and sensing devices on a large scale.
关键词： metallic nanolattices,oligomeric polydimethylsiloxane,microcontact printing,hydroxyl-functional poly(2-vinyl pyridine),gold,wrinkled stamps,nanoparticle assembly,polydimethylsiloxane wrinkles
更新于2025-09-23 15:19:57
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Microsecond Resolved Infrared Spectroelectrochemistry Using Dual Frequency Comb IR Lasers
摘要： A dual infrared frequency comb spectrometer with heterodyne detection has been used to perform time resolved electrochemical attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). The measurement of the potential dependent desorption of a monolayer of a pyridine derivative (4-dimethylaminopyridine, DMAP) with time resolution as high as 4 μs was achieved without the use of step-scan interferometry. An analysis of the detection limit of the method as a function of both time resolution and measurement co-additions is provided and compared to step-scan experiments of an equivalent system. Dual frequency comb spectroscopy is shown to be highly amenable to time-resolved ATR-SEIRAS. Microsecond resolved spectra can be obtained with high spectral resolution and fractional monolayer detection limits in a total experimental duration that is two orders of magnitude less than the equivalent step-scan experiment.
关键词： 4-dimethyamino pyridine (DMAP),noise analysis,Dual frequency comb spectroscopy,time resolved spectroelectrochemistry,RC constant,attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS),detection limit
更新于2025-09-19 17:13:59
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Structural isomers of 9-(pyridin-2-yl)-9H-carbazole in combination with 9a?2H-9,3':6a?2,9a?3-tercarbazole and their application to high efficiency solution processed green TADF OLEDs
摘要： Two host materials, CzPy2TCz and CzPy3TCz, were designed as structural isomers and synthesized to achieve high efficiency thermally activated delayed fluorescence-organic light emitting diodes (TADF-OLEDs). The design strategy involved introducing a pyridine group into the core structure as an electron-withdrawing unit and varying the substitution position of tercarbazole (TCz). To realize green TADF-OLED, the two host materials synthesized in this study have excellent thermal stability and high excited triplet energy (T1 ? 2.95–2.98 eV). The maximum external quantum efficiency and current efficiency values for CzPy2TCz were 23.81% and 80.2 cd/A, respectively and the respective values for CzPy3TCz were 20.27% and 70.1 cd/A, respectively. Structural isomers with carbazole (Cz) and TCz units at the 2,6-position of the pyridine core effectuate better device performance. Consequently, we found that the host materials introduced in this study play an important role in implementing high performing solution-processed green TADF-OLED.
关键词： Thermally activated delayed fluorescence,Organic light-emitting diode,Tercarbazole,Pyridine,Host material,Solution process
更新于2025-09-19 17:13:59