Two new A-D-A porphyrin derivatives,denoted as XLP-I and XLP-II,were prepared through extending theπ-conjugation of thienothiophene-porphyrin center with phenylethynyl bridges and electron-deficient ethylrhodanine te...Two new A-D-A porphyrin derivatives,denoted as XLP-I and XLP-II,were prepared through extending theπ-conjugation of thienothiophene-porphyrin center with phenylethynyl bridges and electron-deficient ethylrhodanine terminal units,and varying the structures of alkyl chain(linear vs branched)on peripheral thienothiophene substitutions of porphyrin rings.Both molecules show strong absorption in UV–visible–near-infrared region,good thermal stability,suitable energy levels,and ordered molecular packing in solid state.In organic solar cells,PC71BM was used as electron acceptor,and porphyrin small molecules were used as electron donors.The device based on XLP-I exhibits a power conversion efficiency(PCE)of 8.30%,an open circuit voltage(Voc)of 0.894 eV,and a fill factor(FF)of 62.1%.In contrast,the device based on XLP-II presents an inferior performance with a PCE of 3.14%,a Voc of 0.847 eV,and a FF of 49.3%.The better performance of XLP-I based device is mainly attributed to its optimized film morphology,excellent absorption,and well-balanced charge transport properties.展开更多
One of the major obstacles of porphyrins is the aggregation-caused quenching(ACQ)of photoluminescence due to the strong intermolecularπ–πinteraction of the planar porphyrin core in the solid state.However,ACQ leads...One of the major obstacles of porphyrins is the aggregation-caused quenching(ACQ)of photoluminescence due to the strong intermolecularπ–πinteraction of the planar porphyrin core in the solid state.However,ACQ leads to the nonradiative deactivation of the photoexcited states which results in short-lived charge-separated states and thus low photoluminescence and singlet quantum yields.This phenomenon would limit the utilization of porphyrins in near-infrared fluorescent bioimaging,photodynamic therapy,photocatalytic hydrogen evolution,electrochemiluminescence,and chiroptical applications.Hence,to address the ACQ property of porphyrins and enhance the performance of the above applications,a limited number of AIEgen-decorated porphyrins have been designed,synthesized,and tested for their applications.It has been found that the introduction of AIEgens,such as tetraphenylethylene,diphenylacrylonitrile,(3,6-bis-(1-methyl-4-vinylpyridinium)-carbazole diiodide,and iridium motif into the porphyrin core,transformed the porphyrins from ACQ to aggregation-induced emission(AIE)in their solid state due to the reduced strong intermolecularπ–πstacking of porphyrins.Consequently,such porphyrins containing AIE features are employed as potential candidates in the above-mentioned applications.In this review,we summarize the AIEgen-decorated porphyrins which have been published to date,and also discuss the benefits of converting porphyrins from ACQ to AIE for enhanced performance within each application.As far as we know,there is no review that summarizes the structures and applications of AIEgen-decorated porphyrins to date.Therefore,we presume that this review would be helpful to design more efficient AIEgen-decorated porphyrins for a wide range of applications in the future.展开更多
Tetraphenylethylene(TPE)-conjugated porphyrin TPE-ZnPF is synthesized in high yield and characterized by single-crystal X-ray diffraction.The propeller-shaped TPE groups not only enable exceptional aggregation-induced...Tetraphenylethylene(TPE)-conjugated porphyrin TPE-ZnPF is synthesized in high yield and characterized by single-crystal X-ray diffraction.The propeller-shaped TPE groups not only enable exceptional aggregation-induced emission(AIE)in the solid state but also abolish the strongπ-πstacking of porphyrin moieties and thus prohibit aggregation-caused quenching(ACQ).TPE-ZnPF aggregates feature longlived photoexcited states,which subsequently suppress non-radiative decay channels and enhance emission intensity.Moreover,its aggregates show more efficient lightharvesting ability due to the Förster resonance energy transfer from the TPE energy donor to the porphyrin core energy acceptor,well-defined nanosphere morphology,and more efficient photoinduced charge separation than the porphyrin Ph-ZnPF,which possesses ACQ and agglomerated morphology.As a result,an excellent photocatalytic hydrogen evolution rate(ηH_(2))of 56.20 mmol g^(‒1)h^(‒1)is recorded for TPE-ZnPF aggregates,which is 94-fold higher than that of the aggregates of Ph-ZnPF(0.60 mmol g^(‒1)h^(‒1))without the TPE groups.展开更多
基金the national key R&D program for international collaboration(No.2021YFE0191500)the National Natural Science Foundation of China(No.51473053)+3 种基金the Natural Science Foundation of Hunan Province(No.2019JJ50603)the Peacock Team Project funding from Shenzhen Science and Technology Innovation Committee(No.KQTD2015033110182370)the Fundamental Research Project funding from Shenzhen Science and Technology Innovation Committee(No.JCYJ 20190809150213448).X.Zhu thanks the financial support from Hong Kong Research Grants Council(HKBU 12304320).
文摘Two new A-D-A porphyrin derivatives,denoted as XLP-I and XLP-II,were prepared through extending theπ-conjugation of thienothiophene-porphyrin center with phenylethynyl bridges and electron-deficient ethylrhodanine terminal units,and varying the structures of alkyl chain(linear vs branched)on peripheral thienothiophene substitutions of porphyrin rings.Both molecules show strong absorption in UV–visible–near-infrared region,good thermal stability,suitable energy levels,and ordered molecular packing in solid state.In organic solar cells,PC71BM was used as electron acceptor,and porphyrin small molecules were used as electron donors.The device based on XLP-I exhibits a power conversion efficiency(PCE)of 8.30%,an open circuit voltage(Voc)of 0.894 eV,and a fill factor(FF)of 62.1%.In contrast,the device based on XLP-II presents an inferior performance with a PCE of 3.14%,a Voc of 0.847 eV,and a FF of 49.3%.The better performance of XLP-I based device is mainly attributed to its optimized film morphology,excellent absorption,and well-balanced charge transport properties.
基金Science,Technology and Innovation Committee of Shenzhen Municipality,Grant/Award Number:JCYJ20180507183413211RGC Senior Research Fellowship Scheme,Grant/Award Number:SRFS2021-5S01+3 种基金National Natural Science Foundation of China,Grant/Award Number:52073242Hong Kong Polytechnic UniversityGeneral Research Fund,Grant/Award Number:12304320Hong Kong Research Grants Council。
文摘One of the major obstacles of porphyrins is the aggregation-caused quenching(ACQ)of photoluminescence due to the strong intermolecularπ–πinteraction of the planar porphyrin core in the solid state.However,ACQ leads to the nonradiative deactivation of the photoexcited states which results in short-lived charge-separated states and thus low photoluminescence and singlet quantum yields.This phenomenon would limit the utilization of porphyrins in near-infrared fluorescent bioimaging,photodynamic therapy,photocatalytic hydrogen evolution,electrochemiluminescence,and chiroptical applications.Hence,to address the ACQ property of porphyrins and enhance the performance of the above applications,a limited number of AIEgen-decorated porphyrins have been designed,synthesized,and tested for their applications.It has been found that the introduction of AIEgens,such as tetraphenylethylene,diphenylacrylonitrile,(3,6-bis-(1-methyl-4-vinylpyridinium)-carbazole diiodide,and iridium motif into the porphyrin core,transformed the porphyrins from ACQ to aggregation-induced emission(AIE)in their solid state due to the reduced strong intermolecularπ–πstacking of porphyrins.Consequently,such porphyrins containing AIE features are employed as potential candidates in the above-mentioned applications.In this review,we summarize the AIEgen-decorated porphyrins which have been published to date,and also discuss the benefits of converting porphyrins from ACQ to AIE for enhanced performance within each application.As far as we know,there is no review that summarizes the structures and applications of AIEgen-decorated porphyrins to date.Therefore,we presume that this review would be helpful to design more efficient AIEgen-decorated porphyrins for a wide range of applications in the future.
基金RGC Senior Research Fellowship Scheme,Grant/Award Number:SRFS2021-5S01National Natural Science Foundation of China,Grant/Award Number:52073242+4 种基金Hong Kong Polytechnic University,Grant/Award Number:YXA2Research Institute for Smart Energy,Grant/Award Number:CDAQMiss Clarea Au for the Endowed Professorship in Energy,Grant/Award Number:847SGeneral Research Fund,Grant/Award Numbers:HKBU 12304320,N_HKBU213/22Hong Kong Research Grants Council,and Initiation Grant for Faculty Niche Research Areas(IG-FNRA),Grant/Award Number:2020/21。
文摘Tetraphenylethylene(TPE)-conjugated porphyrin TPE-ZnPF is synthesized in high yield and characterized by single-crystal X-ray diffraction.The propeller-shaped TPE groups not only enable exceptional aggregation-induced emission(AIE)in the solid state but also abolish the strongπ-πstacking of porphyrin moieties and thus prohibit aggregation-caused quenching(ACQ).TPE-ZnPF aggregates feature longlived photoexcited states,which subsequently suppress non-radiative decay channels and enhance emission intensity.Moreover,its aggregates show more efficient lightharvesting ability due to the Förster resonance energy transfer from the TPE energy donor to the porphyrin core energy acceptor,well-defined nanosphere morphology,and more efficient photoinduced charge separation than the porphyrin Ph-ZnPF,which possesses ACQ and agglomerated morphology.As a result,an excellent photocatalytic hydrogen evolution rate(ηH_(2))of 56.20 mmol g^(‒1)h^(‒1)is recorded for TPE-ZnPF aggregates,which is 94-fold higher than that of the aggregates of Ph-ZnPF(0.60 mmol g^(‒1)h^(‒1))without the TPE groups.