In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for t...In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for the first time. In these polymers, fluorene, 2,7-carbazole, phenothiazine and thiophene are employed as electron-donating groups and PD as electron-withdrawing group. TGA measurements demonstrated that these polymers possess good thermal stability（all above 377 °C）. Very broad absorption spectrum was also obtained from the polymer THTDT（300？850 nm）. CV characterization found that these polymers owned low highest occupied molecular orbital（HOMO） energy levels（？5.39 e V for THTDT, ？5.49 e V for CZTDT and ？5.78 e V for PFTDT） except for PHTDT（？5.17 e V）. The geometry and electronic properties of PFTDT, CZTDT, PHTDT and THTDT were investigated by means of theoretical calculation. All the above advantages demonstrate that PD based polymers could be candidates for electronic devices.展开更多
A series of poly[（methylsilylene ethynylenephenyleneethynylene）-co-（dimethylsilylene ethynylenephenyleneethynylene）]s were synthesized by the incorporation of various ratios of methylsilylene to dimethylsilylene u...A series of poly[（methylsilylene ethynylenephenyleneethynylene）-co-（dimethylsilylene ethynylenephenyleneethynylene）]s were synthesized by the incorporation of various ratios of methylsilylene to dimethylsilylene units into the polymer chain backbone. The resultant copolymers were soluble in a variety of common organic solvents at room temperature. The copolymers were characterized by FT-IR, ^1H-NMR, GPC, rheological analysis, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The results showed that the copolymers exhibited good processability and cured at low temperatures like 200℃. The curing reactions involved in hydrosilylation of Si-H and alkyne groups and the polymerization of alkynes. Td5 （5% weight loss） of the cured copolymers ranged from 629℃ to 686℃, and the decomposition residues of cured copolymers at 1000℃ ranged from 88.1% to 90.9% under nitrogen. Thermal stability of the copolymers increased with the introduction of methylsilylene traits into polymer chains. The cured copolymers were sintered at 1450℃, and the results of X-ray diffraction analysis showed that β-SIC was formed in the sintered products.展开更多
Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elementa...Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1^2- anions connecting the Zn2（O2C）4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2^- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional（3D） supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.展开更多
To enhance the power conversion efficiency(PCE)of organic photovoltaic(OPV)cells,the identification of high-performance polymer/macromolecule materials and understanding their relationship with photovoltaic performanc...To enhance the power conversion efficiency(PCE)of organic photovoltaic(OPV)cells,the identification of high-performance polymer/macromolecule materials and understanding their relationship with photovoltaic performance before synthesis are critical objectives.In this study,we developed five algorithms using a dataset of 1343 experimentally validated OPV NFA acceptor materials.The random forest(RF)algorithm exhibited the best predictive performance for material design and screening.Additionally,we explored a newly developed polymer/macromolecule structure expression,polymer-unit fingerprint(PUFp),which outperformed the molecular access system(MACCS)across diverse machine learning(ML)algorithms.PUFp facilitated the interpretability of structure-property relationships,enabling PCE predictions of conjugated polymers/macromolecules formed by the combination of donor(D)and acceptor(A)units.Our PUFp-ML model efficiently preevaluated and classified numerous acceptor materials,identifying and screening the two most promising NFA candidates.The proposed framework demonstrates the ability to design novel materials based on PUFp-ML-established feature/substructure-property relationships,providing rational design guidelines for developing high-performanceOPV acceptors.These methodologies are transferable to donor materials,thereby supporting accelerated material discovery and offering insights for designing innovative OPV materials.展开更多
基金financially supported by the Research Program of 973 Program(No.2014CB643506)the National Natural Science Foundation of China(No.21401053)+2 种基金Project of Scientific Research and Development of Xiangyang(Year of 2013)Open Foundation of Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices(HLOM141003)Opening Project of Guangxi Colleges and Universities Key Laboratory of Beibu Gulf Oil and Natural Gas Resource Effective Utilization(No.2014KLOG03)
文摘In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for the first time. In these polymers, fluorene, 2,7-carbazole, phenothiazine and thiophene are employed as electron-donating groups and PD as electron-withdrawing group. TGA measurements demonstrated that these polymers possess good thermal stability（all above 377 °C）. Very broad absorption spectrum was also obtained from the polymer THTDT（300？850 nm）. CV characterization found that these polymers owned low highest occupied molecular orbital（HOMO） energy levels（？5.39 e V for THTDT, ？5.49 e V for CZTDT and ？5.78 e V for PFTDT） except for PHTDT（？5.17 e V）. The geometry and electronic properties of PFTDT, CZTDT, PHTDT and THTDT were investigated by means of theoretical calculation. All the above advantages demonstrate that PD based polymers could be candidates for electronic devices.
基金supported by the National High Technology Research and Development Program of China (No.2002-305205)the Special Material Project Program of China(No.51312)Key Project of Science and Technology Foundation of China(9140-12011308)
文摘A series of poly[（methylsilylene ethynylenephenyleneethynylene）-co-（dimethylsilylene ethynylenephenyleneethynylene）]s were synthesized by the incorporation of various ratios of methylsilylene to dimethylsilylene units into the polymer chain backbone. The resultant copolymers were soluble in a variety of common organic solvents at room temperature. The copolymers were characterized by FT-IR, ^1H-NMR, GPC, rheological analysis, differential scanning calorimetry （DSC） and thermogravimetric analysis （TGA）. The results showed that the copolymers exhibited good processability and cured at low temperatures like 200℃. The curing reactions involved in hydrosilylation of Si-H and alkyne groups and the polymerization of alkynes. Td5 （5% weight loss） of the cured copolymers ranged from 629℃ to 686℃, and the decomposition residues of cured copolymers at 1000℃ ranged from 88.1% to 90.9% under nitrogen. Thermal stability of the copolymers increased with the introduction of methylsilylene traits into polymer chains. The cured copolymers were sintered at 1450℃, and the results of X-ray diffraction analysis showed that β-SIC was formed in the sintered products.
基金Supported by the National Natural Science Foundation of China(No.21301035)
文摘Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1^2- anions connecting the Zn2（O2C）4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2^- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional（3D） supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.
基金support was provided by the National Natural Science Foundation of China(92463310,92163212,52473235,52472213,22179062,52125202,and U24A2065)National Key R&D Program of China(2022YFA1203400)+3 种基金High Level of Special Funds(G03050K002)Guangdong Provincial Key Laboratory of Computational Science and Material Design(2019B030301001)the Natural Science Foundation of Jiangsu Province(BK20230035)Computing resources were supported by the Center for Computational Science and Engineering at Southern University of Science and Technology.
文摘To enhance the power conversion efficiency(PCE)of organic photovoltaic(OPV)cells,the identification of high-performance polymer/macromolecule materials and understanding their relationship with photovoltaic performance before synthesis are critical objectives.In this study,we developed five algorithms using a dataset of 1343 experimentally validated OPV NFA acceptor materials.The random forest(RF)algorithm exhibited the best predictive performance for material design and screening.Additionally,we explored a newly developed polymer/macromolecule structure expression,polymer-unit fingerprint(PUFp),which outperformed the molecular access system(MACCS)across diverse machine learning(ML)algorithms.PUFp facilitated the interpretability of structure-property relationships,enabling PCE predictions of conjugated polymers/macromolecules formed by the combination of donor(D)and acceptor(A)units.Our PUFp-ML model efficiently preevaluated and classified numerous acceptor materials,identifying and screening the two most promising NFA candidates.The proposed framework demonstrates the ability to design novel materials based on PUFp-ML-established feature/substructure-property relationships,providing rational design guidelines for developing high-performanceOPV acceptors.These methodologies are transferable to donor materials,thereby supporting accelerated material discovery and offering insights for designing innovative OPV materials.
