Solution-processed conducting polymers(CPs)are emerging as promising multifunctional materials and are motivating the development of several electronic applications.However,there are fewer highperformance electron con...Solution-processed conducting polymers(CPs)are emerging as promising multifunctional materials and are motivating the development of several electronic applications.However,there are fewer highperformance electron conduction-dominated n-type CPs than p-types.Thus,the exploration of other material designs and synthesis methods is required.Accordingly,we developed a facile metal catalystfree method by combining polymerization and in situ n-doping to produce an n-type conducting polymer,poly(benzodithiophenedione)(PBTDO).The doping procedure enabled interaction between the charged conjugated backbones and solvent,dimethyl sulfoxide,making the doped conducting polymer soluble without the assistance of side chains or surfactants.PBTDO exhibited an extremely low-lying reduction level,moderate conductivity,and good air stability with potential applications in n-type organic thermoelectric devices.Moreover,it was found that the in situ doping efficiency in the reaction was highly dependent on the energy level and backbone planarity.Doping cannot occur for polymers with a high lowest unoccupied molecular orbital level and distorted conjugated chains prevent a high doping efficiency from being obtained.This study gains deeper insight into the n-doping mechanisms of conjugated polymers,with guidance for the design of highperformance n-type CPs.展开更多
The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of th...The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.展开更多
A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-...A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-phenylenediamine) (2). Poly N, N′-dithiobis (1,3-phenylenediamine) (3) was prepared by electrochemical polymerization of compound 2 and its basic electrochemical behavior is discussed.展开更多
Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability an...Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability and low thermal conductivity.However,it is challenging to obtain high-performance organic thermoelectric materials because of the low intrinsic carrier concentration of organic semiconductors.The main method to control the carrier concentration of polymers is the chemical doping process by charge transfer between polymer and dopant.Therefore,the deep understanding of doping mechanisms from the point view of chemical structure has been highly desired to overcome the bottlenecks in polymeric thermoelectrics.In this contribution,we will briefly review the recently emerging progress for discovering the structure–property relationship of organic thermoelectric materials with high performance.Highlights include some achievements about doping strategies to effectively modulate the carrier concentration,the design rules of building blocks and side chains to enhance charge transport and improve the doping efficiency.Finally,we will give our viewpoints on the challenges and opportunities in the field of polymer thermoelectric materials.展开更多
I. INTRODUCTION Electrical conductive polymers have attracted considerable attention since the metallic conducting polyacetylene was reported. A relatively large number of conjugated polymers are now known which can b...I. INTRODUCTION Electrical conductive polymers have attracted considerable attention since the metallic conducting polyacetylene was reported. A relatively large number of conjugated polymers are now known which can be doped with either strong electron acceptors or donors to yield conducting complexes. The preparation of conducting polymer is usually展开更多
Based on experimental data, the doping and conductive characters of conjugated polymershaving conjugated triple bond have been analyzed in detail, the doping mechanism for poly-diacetylenes (PDA’s) has been explored ...Based on experimental data, the doping and conductive characters of conjugated polymershaving conjugated triple bond have been analyzed in detail, the doping mechanism for poly-diacetylenes (PDA’s) has been explored preliminarily. A doping model is presented in thelight of structural phase transition. The energy required for causing structural phasetransition of chain segment is estimated. The reason why polydiacetylene crystal dopingfailed is explained.展开更多
The title polymer PCuS4Pz was synthesized by reaction of 2,3-dicyano-5,6-dihydro-1,4-dithiin,pyromellitic dianhydride and urea with cuprous salt in optimized gentle method.The structure and properties of the PCuS4Pz w...The title polymer PCuS4Pz was synthesized by reaction of 2,3-dicyano-5,6-dihydro-1,4-dithiin,pyromellitic dianhydride and urea with cuprous salt in optimized gentle method.The structure and properties of the PCuS4Pz were characterized by elemental analysis,X-ray powder diffraction,IR,UV-Vis,fluorescence and EPR spectra and variable-temperature magnetic susceptibility.The polymer is black sublimable crystallite and the degree of polymerization has been found to be n>4.The PCuS4Pz in H2SO4 exhibits intensive absorption bands at 236,342,656 and 767 nm and intensive fluorescence band at 410 nm or 464 nm under the excitation of the ultraviolet light of a determined wavelength at room temperature.It has been found that the polymer exhibits a weaker antiferromag-netic interaction (J=-2.cm-1,εff=1.68 B.M.) with an apparent spin S<1/2 in the ground state and its conductivity 298K is 1.01×10-5 S-cm-1 at 13.73 MPa.展开更多
基金grant from the Ministry of Science and Technology of the People’s Republic of China(MOST),the Basic and Applied Basic Research Major Program of Guangdong Province(grant no.2019B030302007)the National Natural Science Foundation of China(grant no.U21A6002)the Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials(grant no.2019B121205002).
文摘Solution-processed conducting polymers(CPs)are emerging as promising multifunctional materials and are motivating the development of several electronic applications.However,there are fewer highperformance electron conduction-dominated n-type CPs than p-types.Thus,the exploration of other material designs and synthesis methods is required.Accordingly,we developed a facile metal catalystfree method by combining polymerization and in situ n-doping to produce an n-type conducting polymer,poly(benzodithiophenedione)(PBTDO).The doping procedure enabled interaction between the charged conjugated backbones and solvent,dimethyl sulfoxide,making the doped conducting polymer soluble without the assistance of side chains or surfactants.PBTDO exhibited an extremely low-lying reduction level,moderate conductivity,and good air stability with potential applications in n-type organic thermoelectric devices.Moreover,it was found that the in situ doping efficiency in the reaction was highly dependent on the energy level and backbone planarity.Doping cannot occur for polymers with a high lowest unoccupied molecular orbital level and distorted conjugated chains prevent a high doping efficiency from being obtained.This study gains deeper insight into the n-doping mechanisms of conjugated polymers,with guidance for the design of highperformance n-type CPs.
文摘The title polymers PMS 8Pz,M=Mn Ⅱ,Fe Ⅱ,Co Ⅱ,Ni Ⅱ,Cu Ⅱ,Zn Ⅱ,were synthesized by teaction of 2,3,5,6 tetracyano 1,4 dithiin with corresponding metal salts ,respectively.The styucture and properties of these polyers were characterized by elemental analysis,transmission electron microscope,DTA,IR, UV Vis,fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ 298K of these polymers is in the range of 10 -9 ￣10 -3 S · cm -1 under pressure 10.63 MPa and incremental in the metal orderMn < Co<Fe<Zn<Cu<Ni.\ The photosensitivity of the MS 8Pz to the CdS PVA films is incremental in the metal order Zn < Mn < Co < Fe < Cu < Ni.
文摘A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-phenylenediamine) (2). Poly N, N′-dithiobis (1,3-phenylenediamine) (3) was prepared by electrochemical polymerization of compound 2 and its basic electrochemical behavior is discussed.
基金supported by the National Natural Science Foundation of China(Grant No.21905294)the Shanghai Sailing Program。
文摘Organic semiconductors,especially polymer semiconductors,have attracted extensive attention as organic thermoelectric materials due to their capabilities for flexibility,low-cost fabrication,solution processability and low thermal conductivity.However,it is challenging to obtain high-performance organic thermoelectric materials because of the low intrinsic carrier concentration of organic semiconductors.The main method to control the carrier concentration of polymers is the chemical doping process by charge transfer between polymer and dopant.Therefore,the deep understanding of doping mechanisms from the point view of chemical structure has been highly desired to overcome the bottlenecks in polymeric thermoelectrics.In this contribution,we will briefly review the recently emerging progress for discovering the structure–property relationship of organic thermoelectric materials with high performance.Highlights include some achievements about doping strategies to effectively modulate the carrier concentration,the design rules of building blocks and side chains to enhance charge transport and improve the doping efficiency.Finally,we will give our viewpoints on the challenges and opportunities in the field of polymer thermoelectric materials.
基金Project supported by the National Natural Science Foundation of China
文摘I. INTRODUCTION Electrical conductive polymers have attracted considerable attention since the metallic conducting polyacetylene was reported. A relatively large number of conjugated polymers are now known which can be doped with either strong electron acceptors or donors to yield conducting complexes. The preparation of conducting polymer is usually
基金Project supported by the National Natural Science Foundation of China.
文摘Based on experimental data, the doping and conductive characters of conjugated polymershaving conjugated triple bond have been analyzed in detail, the doping mechanism for poly-diacetylenes (PDA’s) has been explored preliminarily. A doping model is presented in thelight of structural phase transition. The energy required for causing structural phasetransition of chain segment is estimated. The reason why polydiacetylene crystal dopingfailed is explained.
基金Project (No. 107981033) supported by the National Natural Science Foundation of China
文摘The title polymer PCuS4Pz was synthesized by reaction of 2,3-dicyano-5,6-dihydro-1,4-dithiin,pyromellitic dianhydride and urea with cuprous salt in optimized gentle method.The structure and properties of the PCuS4Pz were characterized by elemental analysis,X-ray powder diffraction,IR,UV-Vis,fluorescence and EPR spectra and variable-temperature magnetic susceptibility.The polymer is black sublimable crystallite and the degree of polymerization has been found to be n>4.The PCuS4Pz in H2SO4 exhibits intensive absorption bands at 236,342,656 and 767 nm and intensive fluorescence band at 410 nm or 464 nm under the excitation of the ultraviolet light of a determined wavelength at room temperature.It has been found that the polymer exhibits a weaker antiferromag-netic interaction (J=-2.cm-1,εff=1.68 B.M.) with an apparent spin S<1/2 in the ground state and its conductivity 298K is 1.01×10-5 S-cm-1 at 13.73 MPa.
