The investigation of n-type doping holds a significant interest for the application of thermoelectrics.Herein,the doping of an indandione-terminated compound Q-4F with a singlet open-shell ground state was studied usi...The investigation of n-type doping holds a significant interest for the application of thermoelectrics.Herein,the doping of an indandione-terminated compound Q-4F with a singlet open-shell ground state was studied using two n-dopants N-DMBI and LCV.Both of these two dopants can effectively dope Q-4F due to the large offset between the singly occupied molecular orbital(SOMO)of dopants and the lowest unoccupied molecular orbital(LUMO)of Q-4F.N-DMBI has a higher doping ability than LCV as demonstrated by the UV-vis-NIR and EPR measurements.However,in comparison to N-DMBI doped Q-4F,LCV doped system exhibits much higher electrical conductivity and power factor due to its unperturbed molecular packing and favorable morphology after doping.The optimal conductivity of LCV doped Q-4F is 7.16×10^(-2)±0.16 S·cm^(-1) and the highest power factor reaches 12.3±0.85μW·m–1·K^(-2).These results demonstrate that the modulation of n-dopants is a powerful strategy to balance the doping efficiency and microstructure toward a maximum thermoelectric performance.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
The growing demand for waste heat energy recovery from electronic devices,solar energy,and industrial production has led to increased attention on thermoelectric materials.In the past decades,significant progress has ...The growing demand for waste heat energy recovery from electronic devices,solar energy,and industrial production has led to increased attention on thermoelectric materials.In the past decades,significant progress has been achieved in inorganic thermoelectric materials.Moreover,flexible,lightweight,and bio-friendly organic thermoelectric(OTE)materials have emerged as promising candidates for thermoelectric devices.In particular,quinoidal conjugated small molecules and polymers with high mobility are suitable for thermoelectric conversion.Such kind of materials have gained increasing research interest due to their unique structural features and characteristics of polarons’delocalization.Concurrently,quinoidal materials with high mobility and conductivity have been developed,and their use for thermoelectric conversion has been increasingly reported.This perspective summarizes the recent advancements in the design and synthesis of quinoidal conjugated small molecules and polymers,their advantages for thermoelectric conversion,and the latest reports on their charge carrier transport mechanisms.Moreover,to further enhance the TE performances of quinoidal materials,the existing challenges are discussed and the future developments are also outlooked.展开更多
Comprehensive Summary Conjugated polymers(CPs)containing quinoidal units are promising in n-type organic thermoelectric materials because of their deep-positioned lowest unoccupied molecular orbital(LUMO)energy levels...Comprehensive Summary Conjugated polymers(CPs)containing quinoidal units are promising in n-type organic thermoelectric materials because of their deep-positioned lowest unoccupied molecular orbital(LUMO)energy levels and planar conjugated backbones.Herein,three CPs have been synthesized by copolymerizing an indandione-terminated quinoidal unit with bithiophene derivatives.Owning to the high electron affinity of the indandione-terminated quinoidal unit,all polymers showed deep LUMO energy levels below-4.10 eV.Incorporating electron-withdrawing substituents(F or CN)on the bithiophene comonomer can further downshift the LUMO energy levels.As a result,a more efficient n-doping process can be realized when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine(N-DMBI)as the dopant.Ultimately,the polymer with CN substituents delivered the best thermoelectric performance with a power factor of up to 2.14μW·m^(−1)·K^(−2),because it possessed the lowest LUMO energy level among the three CPs.This work highlights that the modulation of LUMO energy level is an effective strategy to optimize the thermoelectric performance of CPs.展开更多
Singlet fission(SF)has attracted much attention on account of its great potential for applications in high efficiency solar energy conversion.The major roadblock to realize this potential is rooted in the limited avai...Singlet fission(SF)has attracted much attention on account of its great potential for applications in high efficiency solar energy conversion.The major roadblock to realize this potential is rooted in the limited availability of practical SF material with strong absorption,suitable triplet energy level,an efficient SF process,and good chemical stability.Quinoidal structures feature an innate diradical character,which endows these skeletons with SF potential yet results in some structural instability.展开更多
CPDT-TCNQ and its derivatives are good candidates for charge-transfer acceptors. In this work, the electronic ground and excited states of CPDT-TCNQ as well as its difluoro and dimethyl derivatives are studied. The gr...CPDT-TCNQ and its derivatives are good candidates for charge-transfer acceptors. In this work, the electronic ground and excited states of CPDT-TCNQ as well as its difluoro and dimethyl derivatives are studied. The ground state optimized structures and energies were obtained using a restricted (closed-shell) density functional theory (DFT) as approximated by the various hybrid functionals (RB3LYP, RB3P86, RB3PW91). The 6-31G** and 6-31+G** basis sets were employed in calculations. All derivatives are planar and exhibit a quinoid structure in their electronic ground states. The energy and oscillator strength of the first 15 singlet-singlet electronic transitions have been investigated by applying the dine-dependent density functional theory (TD-DFT) approximations to the correspondingly optimized ground state geometries. The results show the strongest absorption in electronic spectra of molecules due to the HOMO-LUMO electronic transition of the thiophene backbone.展开更多
Organic diradicaloids have unusual open-shell nature and properties and are promising materials for organic electronics,spintronics,energy storage and nonlinear optics.In this review,we focus on indeno-type organic di...Organic diradicaloids have unusual open-shell nature and properties and are promising materials for organic electronics,spintronics,energy storage and nonlinear optics.In this review,we focus on indeno-type organic diradicaloids and summarize their molecular design and synthesis,as well as topological structures,open-shell characters and diradical properties.The molecular systems are classified into indenofluorenes and diindenoacenes,indeno-based molecules with one-dimensional,two-dimensional and unique topological structures,and heterocyclic indeno-based molecules.By constructing these various topologicalπ-skeletons with tunable conjugation modes and variation of atomic composition,their key open-shell parameters,such as diradical characters and singlet-triplet energy gaps,along with the optical,electronic and magnetic properties,as well as stabilities are efficiently modulated.More attention may be paid to accurate computational analysis,rational design and synthesis,and novel functions of indeno-type diradicaloids,which will promote the development of radical chemistry and materials.展开更多
The employment of an intrinsic quinoidal building block,benzodipyrrolidone(BDP),on constructing conjugated polymers(PBDP-2F and PBDP-2CN)with high electron mobility and unipolar transport characteristic in polyethylen...The employment of an intrinsic quinoidal building block,benzodipyrrolidone(BDP),on constructing conjugated polymers(PBDP-2F and PBDP-2CN)with high electron mobility and unipolar transport characteristic in polyethylenimine ethoxylated(PEIE)modified organic field-effect transistors(OFETs)is reported.The intrinsic quinoidal characteristic and excellent coplanarity of BDP can lower the lowest unoccupied molecular orbital(LUMO)levels and improve ordered interchain packing of the resulting polymers in solid states,which are favorable for electron-injection and transport.By using PEIE as the interlayer to block the hole injection,unipolar n-type transport characteristics with high electron mobility of 0.58 and 1.01 cm^(2) V^(-1)s^(-1)were achieved by the OFETs based on PBDP-2F and PBDP-2CN,respectively.More importantly,the extracted mobilities are highly reliable with the reliability factor of above 80%.To the best of our knowledge,PBDP-2CN is the very first quinoid-based conjugated polymer with reliable electron mobility exceeding 1 cm^(2) V^(-1)s^(-1).This work represents a significant step in exploring intrinsic quinoidal CPs for application in n-channel OFETs and logic complementary circuits.展开更多
The ubiquitous distribution of halogenated aromatic compounds(XAr) coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced ox...The ubiquitous distribution of halogenated aromatic compounds(XAr) coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes(AOPs) have been considered as an"environmentally-friendly" technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals(UOH) by halogenated quinones and H_2O_2, we found, unexpectedly, that an unprecedented UOH-dependent two-step intrinsic chemiluminescene(CL) can be produced by H_2O_2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all UOH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure–activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that UOH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive,simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants.展开更多
基金supported by the National Key R&D Program of China(2021YFA0717900)the National Natural Science Foundation of China(Nos.22222506,52073209,and 52121002)and the Fundamental Research Funds for the Central Universities.
文摘The investigation of n-type doping holds a significant interest for the application of thermoelectrics.Herein,the doping of an indandione-terminated compound Q-4F with a singlet open-shell ground state was studied using two n-dopants N-DMBI and LCV.Both of these two dopants can effectively dope Q-4F due to the large offset between the singly occupied molecular orbital(SOMO)of dopants and the lowest unoccupied molecular orbital(LUMO)of Q-4F.N-DMBI has a higher doping ability than LCV as demonstrated by the UV-vis-NIR and EPR measurements.However,in comparison to N-DMBI doped Q-4F,LCV doped system exhibits much higher electrical conductivity and power factor due to its unperturbed molecular packing and favorable morphology after doping.The optimal conductivity of LCV doped Q-4F is 7.16×10^(-2)±0.16 S·cm^(-1) and the highest power factor reaches 12.3±0.85μW·m–1·K^(-2).These results demonstrate that the modulation of n-dopants is a powerful strategy to balance the doping efficiency and microstructure toward a maximum thermoelectric performance.
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he National Key R&D Program of China(Nos.2019YFA0705900 and 2017YFA0204701)the National Natural Science Foundation of China(Nos.52225305 and 22175187)+1 种基金the International Partnership Program of the Chinese Academy of Sciences(No.027GJHZ2022036GC)the Natural Science Foundation of Changsha(No.kq2208024).
文摘The growing demand for waste heat energy recovery from electronic devices,solar energy,and industrial production has led to increased attention on thermoelectric materials.In the past decades,significant progress has been achieved in inorganic thermoelectric materials.Moreover,flexible,lightweight,and bio-friendly organic thermoelectric(OTE)materials have emerged as promising candidates for thermoelectric devices.In particular,quinoidal conjugated small molecules and polymers with high mobility are suitable for thermoelectric conversion.Such kind of materials have gained increasing research interest due to their unique structural features and characteristics of polarons’delocalization.Concurrently,quinoidal materials with high mobility and conductivity have been developed,and their use for thermoelectric conversion has been increasingly reported.This perspective summarizes the recent advancements in the design and synthesis of quinoidal conjugated small molecules and polymers,their advantages for thermoelectric conversion,and the latest reports on their charge carrier transport mechanisms.Moreover,to further enhance the TE performances of quinoidal materials,the existing challenges are discussed and the future developments are also outlooked.
基金supported by National Key R&D Program of China(2021YFA0717900)National Natural Science Foundation of China(52073209,52121002 and 22222506)the Fundamental Research Funds forthe Central Universities.
文摘Comprehensive Summary Conjugated polymers(CPs)containing quinoidal units are promising in n-type organic thermoelectric materials because of their deep-positioned lowest unoccupied molecular orbital(LUMO)energy levels and planar conjugated backbones.Herein,three CPs have been synthesized by copolymerizing an indandione-terminated quinoidal unit with bithiophene derivatives.Owning to the high electron affinity of the indandione-terminated quinoidal unit,all polymers showed deep LUMO energy levels below-4.10 eV.Incorporating electron-withdrawing substituents(F or CN)on the bithiophene comonomer can further downshift the LUMO energy levels.As a result,a more efficient n-doping process can be realized when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine(N-DMBI)as the dopant.Ultimately,the polymer with CN substituents delivered the best thermoelectric performance with a power factor of up to 2.14μW·m^(−1)·K^(−2),because it possessed the lowest LUMO energy level among the three CPs.This work highlights that the modulation of LUMO energy level is an effective strategy to optimize the thermoelectric performance of CPs.
基金supported by the National Natural Science Foundation of China(nos.22005210,21833005,and 21833006).
文摘Singlet fission(SF)has attracted much attention on account of its great potential for applications in high efficiency solar energy conversion.The major roadblock to realize this potential is rooted in the limited availability of practical SF material with strong absorption,suitable triplet energy level,an efficient SF process,and good chemical stability.Quinoidal structures feature an innate diradical character,which endows these skeletons with SF potential yet results in some structural instability.
基金This work was supported by the Science Research Foundation of Yangtze University
文摘CPDT-TCNQ and its derivatives are good candidates for charge-transfer acceptors. In this work, the electronic ground and excited states of CPDT-TCNQ as well as its difluoro and dimethyl derivatives are studied. The ground state optimized structures and energies were obtained using a restricted (closed-shell) density functional theory (DFT) as approximated by the various hybrid functionals (RB3LYP, RB3P86, RB3PW91). The 6-31G** and 6-31+G** basis sets were employed in calculations. All derivatives are planar and exhibit a quinoid structure in their electronic ground states. The energy and oscillator strength of the first 15 singlet-singlet electronic transitions have been investigated by applying the dine-dependent density functional theory (TD-DFT) approximations to the correspondingly optimized ground state geometries. The results show the strongest absorption in electronic spectra of molecules due to the HOMO-LUMO electronic transition of the thiophene backbone.
基金National Natural Science Foundation of China(No.22175074)Jilin Scientific and Technological Development Program,China(No.20220101054JC).
文摘Organic diradicaloids have unusual open-shell nature and properties and are promising materials for organic electronics,spintronics,energy storage and nonlinear optics.In this review,we focus on indeno-type organic diradicaloids and summarize their molecular design and synthesis,as well as topological structures,open-shell characters and diradical properties.The molecular systems are classified into indenofluorenes and diindenoacenes,indeno-based molecules with one-dimensional,two-dimensional and unique topological structures,and heterocyclic indeno-based molecules.By constructing these various topologicalπ-skeletons with tunable conjugation modes and variation of atomic composition,their key open-shell parameters,such as diradical characters and singlet-triplet energy gaps,along with the optical,electronic and magnetic properties,as well as stabilities are efficiently modulated.More attention may be paid to accurate computational analysis,rational design and synthesis,and novel functions of indeno-type diradicaloids,which will promote the development of radical chemistry and materials.
基金supported by the Ministry of Science and Technology of China(2017YFA0206600,2019YFA0705900)the National Natural Science Foundation of China(21875072,21774093)+2 种基金the Fundamental Research Funds for Central Universities(South China University of Technology,D2190310)Guangdong Innovative and Entrepreneurial Research Team Program(2019ZT08L075)the Open Funds of State Key Laboratory of Fine Chemicals(KF1901)。
文摘The employment of an intrinsic quinoidal building block,benzodipyrrolidone(BDP),on constructing conjugated polymers(PBDP-2F and PBDP-2CN)with high electron mobility and unipolar transport characteristic in polyethylenimine ethoxylated(PEIE)modified organic field-effect transistors(OFETs)is reported.The intrinsic quinoidal characteristic and excellent coplanarity of BDP can lower the lowest unoccupied molecular orbital(LUMO)levels and improve ordered interchain packing of the resulting polymers in solid states,which are favorable for electron-injection and transport.By using PEIE as the interlayer to block the hole injection,unipolar n-type transport characteristics with high electron mobility of 0.58 and 1.01 cm^(2) V^(-1)s^(-1)were achieved by the OFETs based on PBDP-2F and PBDP-2CN,respectively.More importantly,the extracted mobilities are highly reliable with the reliability factor of above 80%.To the best of our knowledge,PBDP-2CN is the very first quinoid-based conjugated polymer with reliable electron mobility exceeding 1 cm^(2) V^(-1)s^(-1).This work represents a significant step in exploring intrinsic quinoidal CPs for application in n-channel OFETs and logic complementary circuits.
基金supported by the Strategic Priority Research Program of CAS(No.XDB01020300)NSF China Grants(Nos.21577149,21477139,21237005 and 21321004)NIH Grants(Nos.ES11497,RR01008 and ES00210)
文摘The ubiquitous distribution of halogenated aromatic compounds(XAr) coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes(AOPs) have been considered as an"environmentally-friendly" technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals(UOH) by halogenated quinones and H_2O_2, we found, unexpectedly, that an unprecedented UOH-dependent two-step intrinsic chemiluminescene(CL) can be produced by H_2O_2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all UOH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure–activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that UOH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive,simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants.