Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their d...Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.展开更多
A series of new silicon-containing poly（p-arylene vinylene）s （PAVs） with anthracene units in the main chain were synthesized by hydrosilylation reaction. The introduction of organosilicon units improved the solubi...A series of new silicon-containing poly（p-arylene vinylene）s （PAVs） with anthracene units in the main chain were synthesized by hydrosilylation reaction. The introduction of organosilicon units improved the solubility of the polymers, and the π-π conjugation of polymeric chains was interrupted. These polymers behaved as blue-green light emitters with their fluorescence maximum at 447-499 nm and quantum yields in the range of 0.28-0.30 in solution.展开更多
Azulene-fused acenes demonstrate enhanced stability,unique aromaticity,and distinctive photophysical properties,rendering them significant in organic electronics.In the present study,we report a new type of nonalterna...Azulene-fused acenes demonstrate enhanced stability,unique aromaticity,and distinctive photophysical properties,rendering them significant in organic electronics.In the present study,we report a new type of nonalternant analogue of pentacene incorporating a non-terminal azulene unit.Aromaticity analyses reveal that the five-membered rings in this analogue exhibit antiaromatic.The extensive conjugated aryl substituents on the acene’s side shift the HOMO distributions from the naphthyl ring and metallacycle to the aryl groups,thereby narrowing the HOMO-LUMO energy gap and enhancing absorptions in the low-energy regions.Furthermore,these fused acenes readily react with base rather than acid,resulting in reversible base/acid stimuli responsiveness.展开更多
Green-emitting iridium(Ⅲ)complexes were synthesised using chlorobridged dimer(ppy)_(2)Ir_(2)Cl_(2)(ppy)_(2),3-hydroxy-2-methyl-γ-pyranone,2-ethyl-3-hydroxy-4-pyranone,and 5-hydroxy-2-(hydroxymethyl)-1,4-pyranone as ...Green-emitting iridium(Ⅲ)complexes were synthesised using chlorobridged dimer(ppy)_(2)Ir_(2)Cl_(2)(ppy)_(2),3-hydroxy-2-methyl-γ-pyranone,2-ethyl-3-hydroxy-4-pyranone,and 5-hydroxy-2-(hydroxymethyl)-1,4-pyranone as the auxiliary ligand.The structure of the target product was characterised by nuclear magnetic resonance spectroscopy(~1H-NMR),infrared spectroscopy(IR)and mass spectrometry(MS),and its thermal stability,photophysical properties and electrochemical properties were investigated.The results show that the decomposition temperatures of Ir1,Ir2 and Ir3 are 349,292 and 200℃,respectively.The maximum emission wavelength of Ir1,Ir2 and Ir3 dissolved in dichloromethane is 491 nm.The HOMO energy level of Ir1,Ir2 and Ir3 are 5.39,-5.38,and-5.30 eV.The LUMO energy levels are-2.86,-2.85,and-2.80 eV,respectively.展开更多
Quinoidalπ-conjugated structures,a kind of fundamental subunits for organicπ-systems,may produce some intriguing optical,electronic and magnetic properties of polycyclic hydrocarbons(PHs).Herein,we report two thieno...Quinoidalπ-conjugated structures,a kind of fundamental subunits for organicπ-systems,may produce some intriguing optical,electronic and magnetic properties of polycyclic hydrocarbons(PHs).Herein,we report two thienothiophene-centered ladder-type polycyclic molecules(1 and 2),which possess one quinoidal thienothiophene moiety and two para-quinodimethane(p-QDM)subunits,respectively.As theoretically and experimentally studied,while 1 is a fully closed-shell molecule,2 owns an open-shell structure along with partial contribution of tetraradical state that is induced by the resonance of p-QDM.Moreover,although 2 has a largerπ-conjugated skeleton and open-shell electronic state,it exhibits larger bandgap and blue-shifted absorption.On the other hand,the reversible oxidation activity of 1 enables the preparation of its dication 1^(2+),and the studies on its single-crystal and aromatic structures demonstrate that its two positive charges are delocalized onto the oxygen atoms,thus achieving fullyπ-extended structure and near-infrared absorption.This study not only gains insight into quinoidalπ-subunits,but also provides an important basis for the development of antiaromatic and open-shellπ-electron materials.展开更多
Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers...Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.展开更多
The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminesce...The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminescence,and so on.However,the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence.Herein,we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine(TPA)at different positions and metal ions and explored their photophysical properties.In the solution state,MLE_(2)based on the 5,5″-positions modification showed the highest PLQYs and PL intensity.With the increase of solvent polarity,MLB2exhibit the largest redshift.In the solid state,from MLA_(2)to MLE_(2),the emission colours are gradually red-shifted from yellow to red.The findings in this work may pave a new way to design functional metallo-complexes,not just for PL properties.展开更多
基金Project supported by the Science Challenge Project(Grant No.TZ2018001)the National Natural Science Foundation of China(Grant Nos.11872058 and 21802036)the Project of State Key Laboratory of Environment-friendly Energy Materials,and Southwest University of Science and Technology(Grant No.21fksy07)。
文摘Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.
基金supported by the National Natural Science Foundation of China(Nos.50673094 and 20774102)
文摘A series of new silicon-containing poly（p-arylene vinylene）s （PAVs） with anthracene units in the main chain were synthesized by hydrosilylation reaction. The introduction of organosilicon units improved the solubility of the polymers, and the π-π conjugation of polymeric chains was interrupted. These polymers behaved as blue-green light emitters with their fluorescence maximum at 447-499 nm and quantum yields in the range of 0.28-0.30 in solution.
基金supported by the National Natural Science Foundation of China(Nos.92156021,22350009,and 22101115)Financial Support for Outstanding Talents Training Fund in Shenzhen,the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)+2 种基金high level of special funds(No.G03050K003)Introduction of Major Talent Projects in Guangdong Province(No.2019CX01C079)supported by the Center for Computational Science and Engineering at SUSTech.
文摘Azulene-fused acenes demonstrate enhanced stability,unique aromaticity,and distinctive photophysical properties,rendering them significant in organic electronics.In the present study,we report a new type of nonalternant analogue of pentacene incorporating a non-terminal azulene unit.Aromaticity analyses reveal that the five-membered rings in this analogue exhibit antiaromatic.The extensive conjugated aryl substituents on the acene’s side shift the HOMO distributions from the naphthyl ring and metallacycle to the aryl groups,thereby narrowing the HOMO-LUMO energy gap and enhancing absorptions in the low-energy regions.Furthermore,these fused acenes readily react with base rather than acid,resulting in reversible base/acid stimuli responsiveness.
文摘Green-emitting iridium(Ⅲ)complexes were synthesised using chlorobridged dimer(ppy)_(2)Ir_(2)Cl_(2)(ppy)_(2),3-hydroxy-2-methyl-γ-pyranone,2-ethyl-3-hydroxy-4-pyranone,and 5-hydroxy-2-(hydroxymethyl)-1,4-pyranone as the auxiliary ligand.The structure of the target product was characterised by nuclear magnetic resonance spectroscopy(~1H-NMR),infrared spectroscopy(IR)and mass spectrometry(MS),and its thermal stability,photophysical properties and electrochemical properties were investigated.The results show that the decomposition temperatures of Ir1,Ir2 and Ir3 are 349,292 and 200℃,respectively.The maximum emission wavelength of Ir1,Ir2 and Ir3 dissolved in dichloromethane is 491 nm.The HOMO energy level of Ir1,Ir2 and Ir3 are 5.39,-5.38,and-5.30 eV.The LUMO energy levels are-2.86,-2.85,and-2.80 eV,respectively.
基金supported by National Natural Science Foundation of China(Nos.22175074 and 52373182)Jilin Scientific and Technological Development Program(No.20220101054JC).
文摘Quinoidalπ-conjugated structures,a kind of fundamental subunits for organicπ-systems,may produce some intriguing optical,electronic and magnetic properties of polycyclic hydrocarbons(PHs).Herein,we report two thienothiophene-centered ladder-type polycyclic molecules(1 and 2),which possess one quinoidal thienothiophene moiety and two para-quinodimethane(p-QDM)subunits,respectively.As theoretically and experimentally studied,while 1 is a fully closed-shell molecule,2 owns an open-shell structure along with partial contribution of tetraradical state that is induced by the resonance of p-QDM.Moreover,although 2 has a largerπ-conjugated skeleton and open-shell electronic state,it exhibits larger bandgap and blue-shifted absorption.On the other hand,the reversible oxidation activity of 1 enables the preparation of its dication 1^(2+),and the studies on its single-crystal and aromatic structures demonstrate that its two positive charges are delocalized onto the oxygen atoms,thus achieving fullyπ-extended structure and near-infrared absorption.This study not only gains insight into quinoidalπ-subunits,but also provides an important basis for the development of antiaromatic and open-shellπ-electron materials.
基金supported by the National Natural Science Foundation of China(Nos.21776207 and 21576195)。
文摘Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.
基金financially supported by the National Natural Science Foundation of China(Nos.22271116 and 22071079 for M.W)Jilin Provincial Science and Technology Department(No.20230101027JC for M.W.)the fellowship of China Postdoctoral Science Foundation(No.2021M701383 for J.S)。
文摘The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminescence,and so on.However,the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence.Herein,we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine(TPA)at different positions and metal ions and explored their photophysical properties.In the solution state,MLE_(2)based on the 5,5″-positions modification showed the highest PLQYs and PL intensity.With the increase of solvent polarity,MLB2exhibit the largest redshift.In the solid state,from MLA_(2)to MLE_(2),the emission colours are gradually red-shifted from yellow to red.The findings in this work may pave a new way to design functional metallo-complexes,not just for PL properties.
