In this work, star-shaped perylene bisimide(PBI) derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were fou...In this work, star-shaped perylene bisimide(PBI) derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies(PCEs) up to 4.27% due to the high short-circuit current density(Jsc) of 8.52 mA/cm^2 and fill factor(FF) of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.展开更多
Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structu...Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.展开更多
To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a fle...To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.展开更多
Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, o...Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.展开更多
The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-...The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-arrangement for the favourable ring-closure mechanism and ethyne addition in each step. The analysis was done by evaluating the energy difference of activation （AE）, entalphy （AH）, Gibbs （AG） of the optimized stable and transition molecules. The reaction temperatures were set at normal （T = 298 K） and combustion （T = 1200 K） condition.展开更多
Luminescent two-photon(2P)absorbing lanthanide(III)complexes hold great promise for microsocpy imaging of biological samples.Conjugating such a complex to well-chosen cell penetrating peptides(CPP)allows its controlle...Luminescent two-photon(2P)absorbing lanthanide(III)complexes hold great promise for microsocpy imaging of biological samples.Conjugating such a complex to well-chosen cell penetrating peptides(CPP)allows its controlled delivery to the cytosol of live cells.However,alkoxy-phenyl-ethynyl-picolinate,one of the best antennae for 2P sensitization of Eu^(3+),undergoes side reactions at its ethynyl group during peptide synthesis or in biological media and thus cannot be used to create such a conjugate.In this article,we evaluate the effect of substituting the ethynyl group by a phenyl one.We describe the synthesis of conjugates of the TAT CPP with Eu^(3+)complexes featuring amido-phenyl-phenyl-picolinamide,alkoxy-phenyl-phenyl-picolinamide and amido-phenyl-phenyl-picolinate ter-aryl antennae and compare their spectroscopic properties to those of analogues with bi-aryl antennae,including the amido-phenyl-picolinamide already used for 2P live cell imaging.The absorption spectrum of the teraryl antennae is red-shifted and better covers the active spectral range for 2P excitation by a Ti-sapphire laser.Among compounds with ter-aryl antennae,those with an amido electron donating group are the most interesting,showing brightness ca.4 times higher than their bi-aryl counterparts,and similar to the ethynyl-containing antenna.2P microscopy imaging of live cells incubated with the TAT-Eu^(3+)conjugate and dFFLIPTAT,a non-luminescent CPP that promotes cytosolic delivery,showed diffuse cytosolic staining of the Eu^(3+)probe.The ter-aryl-based probes showed superior performances compared to bi-aryl,with ca.80%of the cells showing Eu^(3+)staining of the cytosol.展开更多
The design,synthesis and characterization of two new triptycene-containing ditopic Pt(Ⅱ)organometallic complexes is being reported.These complexes comprise of two peripheral bis(trans-trialkylphosphine)-platinum unit...The design,synthesis and characterization of two new triptycene-containing ditopic Pt(Ⅱ)organometallic complexes is being reported.These complexes comprise of two peripheral bis(trans-trialkylphosphine)-platinum units either directly σ-bonded to the central triptycene moiety or connected via a bridging ethynyl spacer linkage.The potential utility of these organometallic complexes as ditopic acceptor building blocks for the construction of neutral metallasupramolecular macrocycles containing the triptycene motif is explored.Triptycene motif containing supramolecules were characterized using multinuclear NMR(including ^(1)H DOSY),mass spectrometry(MALDI-TOF-MS)and elemental analyses.While the selfassembly of a longer acceptor linker with a terephthalate group results in the formation of a[3+3]selfassembled macrocycle,the use of a relatively shorter acceptor linker yields the corresponding[2+2]supramolecular framework.The shapes and dimensions of these supramolecular structures were also predicted by geometry optimization using PM6 semiempirical molecular orbital methods and the results corroborate well with the experimental observations.These two self-assembled macrocycles are unique examples of triptycene-based neutral“platinamacrocycles”reported in the literature to date.An investigation as to how the shape and size of the resulting discrete supramolecular framework is affected upon changing the length and rigidity of the triptycene-based acceptor linkers is discussed.展开更多
Through the elaborate design of an ethynyl-naphthalimide ligand with a phenylethylamino group as chiral origin,we report the synthesis,characterization,photophysical and electroluminescence properties of a pair of chi...Through the elaborate design of an ethynyl-naphthalimide ligand with a phenylethylamino group as chiral origin,we report the synthesis,characterization,photophysical and electroluminescence properties of a pair of chiral PtAu_(2)trinuclear clusters with high-efficiency circularly polarized narrow-band red emission.As demonstrated by experimental and theoretical studies,the phosphorescence of the trinuclear cluster originates from the intraligand(^(3)IL)triplet state of ethynyl-naphthalimide having a chiral benzylamino moiety.The R/S-PtAu_(2)clusters exhibit significant circularly polarized luminescence(CPL)properties with an asymmetry factor of approximately±1×10^(-3).Organic light-emitting diodes(OLEDs)based on chiral PtAu_(2)clusters demonstrate circularly polarized electroluminescence(CPEL)performance with an asymmetry factor of approximately±7×10^(-4)and an external quantum efficiency(EQE)of 13.7%.The devices exhibit narrow-band red emission and high color purity with CIE 1931 coordinates of(0.68,0.32)and a full width at half maximum(FWHM)of 29 nm.Both circular dichroism(CD)and CPL studies demonstrate the excellent chiral absorption and emission characteristics of trinuclear cluster enantiomers in the ground state as well as in the excited state.展开更多
Combining spin crossover(SCO)and fluorescence properties could respond to multiple physical stimulus and is meaningful for the development of switches and imaging tools.In this work,we present a new family of neutral ...Combining spin crossover(SCO)and fluorescence properties could respond to multiple physical stimulus and is meaningful for the development of switches and imaging tools.In this work,we present a new family of neutral mononuclear iron(Ⅱ)complexes,denoted as Fe(L^(1-3))_(2) and Fe(L^(3))_(2)·CH_(2)Cl_(2) with N_(4)O_(2) donor sets.These complexes were synthesized employing a series of tridentate Schiff base ligands,which contain an ethynyl group(HL^(1-3)=3-ethynyl-N′-((4-methylpyridin-2-yl)methylene)benzohydrazide(4MePAH-3EyBHZ,HL^(1)),3-ethynyl-N′-((4-methoxylpyridin-2-yl)methylene)benzohydrazide(4OMe-PAH-3EyBHZ,HL^(2)),3-ethynyl-N′-((5-methylpyridin-2-yl)methylene)benzohydrazide(5MePAH-3EyBHZ,HL^(3))).Variable-temperature magnetic susceptibility measurements revealed that Fe(L^(1))_(2) exhibits an abrupt and complete SCO with characteristic temperature T_(1/2↓)=176 K and T_(1/2↑)=178 K;Fe(L^(2))_(2) exhibits an abrupt and complete SCO with T_(1/2↓)=214 K and T_(1/2↑)=219 K;Fe(L^(3))_(2) exhibits an abrupt and complete SCO with T_(1/2↓)=218 K and T_(1/2↑)=226 K.The partial conformational inversion is observed between the high spin and low spin state of Fe(L^(2))_(2) evidenced by the variable-temperature single-crystal X-ray diffraction analysis.An unusual increase of emission intensity was observed in the fluorescence spectra of Fe(L^(1))_(2) and Fe(L^(2))_(2) during the heating SCO process.These findings are both valuable in the study of spin-fluorescence interaction and synthesis of new multifunctional SCO complexes.展开更多
基金supported by the Recruitment Program of Global Youth Experts of Chinasupported by the National Natural Science Foundation of China(Nos. 21574138, 51603209 and 91633301)the Strategic Priority Research Program(No. XDB12030200) of the Chinese Academy of Sciences
文摘In this work, star-shaped perylene bisimide(PBI) derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies(PCEs) up to 4.27% due to the high short-circuit current density(Jsc) of 8.52 mA/cm^2 and fill factor(FF) of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.
文摘Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.
基金financially supported by the National Natural Science Foundation of China(Nos.22131005,22201074,22075077 and 21971063)the Fundamental Research Funds for the Central Universities,Program of Shanghai Academic Research Leader(No.20XD1401400)+1 种基金Shanghai Rising-Star Program(No.23QA1402100)Natural Science Foundation of Shanghai(Nos.23ZR1415600,22ZR1416100).
文摘To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.
基金financially supported by the National Natural Science Foundation of China(No.21674126)the"Strategic Priority Research Program"(No.XDB12010100)the Shanghai Science and Technology Committee(No.16JC1400603)
文摘Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.
文摘The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-arrangement for the favourable ring-closure mechanism and ethyne addition in each step. The analysis was done by evaluating the energy difference of activation （AE）, entalphy （AH）, Gibbs （AG） of the optimized stable and transition molecules. The reaction temperatures were set at normal （T = 298 K） and combustion （T = 1200 K） condition.
基金Agence Nationale de la Recherche(ANR-18-CE06-0022 and ANR-21-CE29-0018)the Labex ARCANE,CBH-EUR-GS(ANR-17-EURE-0003)+1 种基金the CEA FOCUS Biomarqueurs program for financial supportthe IBISA-ISdV platform,member of the national infrastructure France-BioImaging supported by the French National Research Agency(ANR-10-INBS-04).
文摘Luminescent two-photon(2P)absorbing lanthanide(III)complexes hold great promise for microsocpy imaging of biological samples.Conjugating such a complex to well-chosen cell penetrating peptides(CPP)allows its controlled delivery to the cytosol of live cells.However,alkoxy-phenyl-ethynyl-picolinate,one of the best antennae for 2P sensitization of Eu^(3+),undergoes side reactions at its ethynyl group during peptide synthesis or in biological media and thus cannot be used to create such a conjugate.In this article,we evaluate the effect of substituting the ethynyl group by a phenyl one.We describe the synthesis of conjugates of the TAT CPP with Eu^(3+)complexes featuring amido-phenyl-phenyl-picolinamide,alkoxy-phenyl-phenyl-picolinamide and amido-phenyl-phenyl-picolinate ter-aryl antennae and compare their spectroscopic properties to those of analogues with bi-aryl antennae,including the amido-phenyl-picolinamide already used for 2P live cell imaging.The absorption spectrum of the teraryl antennae is red-shifted and better covers the active spectral range for 2P excitation by a Ti-sapphire laser.Among compounds with ter-aryl antennae,those with an amido electron donating group are the most interesting,showing brightness ca.4 times higher than their bi-aryl counterparts,and similar to the ethynyl-containing antenna.2P microscopy imaging of live cells incubated with the TAT-Eu^(3+)conjugate and dFFLIPTAT,a non-luminescent CPP that promotes cytosolic delivery,showed diffuse cytosolic staining of the Eu^(3+)probe.The ter-aryl-based probes showed superior performances compared to bi-aryl,with ca.80%of the cells showing Eu^(3+)staining of the cytosol.
基金the Department of Science and Technology,Govt.of India,New Delhi(DST no:SR/FT/CS-028/2009)the Indian Institute of Technology Patna for financial support.
文摘The design,synthesis and characterization of two new triptycene-containing ditopic Pt(Ⅱ)organometallic complexes is being reported.These complexes comprise of two peripheral bis(trans-trialkylphosphine)-platinum units either directly σ-bonded to the central triptycene moiety or connected via a bridging ethynyl spacer linkage.The potential utility of these organometallic complexes as ditopic acceptor building blocks for the construction of neutral metallasupramolecular macrocycles containing the triptycene motif is explored.Triptycene motif containing supramolecules were characterized using multinuclear NMR(including ^(1)H DOSY),mass spectrometry(MALDI-TOF-MS)and elemental analyses.While the selfassembly of a longer acceptor linker with a terephthalate group results in the formation of a[3+3]selfassembled macrocycle,the use of a relatively shorter acceptor linker yields the corresponding[2+2]supramolecular framework.The shapes and dimensions of these supramolecular structures were also predicted by geometry optimization using PM6 semiempirical molecular orbital methods and the results corroborate well with the experimental observations.These two self-assembled macrocycles are unique examples of triptycene-based neutral“platinamacrocycles”reported in the literature to date.An investigation as to how the shape and size of the resulting discrete supramolecular framework is affected upon changing the length and rigidity of the triptycene-based acceptor linkers is discussed.
基金financial support from the National Natural Science Foundation of China(grants 92061202 and 21801242).
文摘Through the elaborate design of an ethynyl-naphthalimide ligand with a phenylethylamino group as chiral origin,we report the synthesis,characterization,photophysical and electroluminescence properties of a pair of chiral PtAu_(2)trinuclear clusters with high-efficiency circularly polarized narrow-band red emission.As demonstrated by experimental and theoretical studies,the phosphorescence of the trinuclear cluster originates from the intraligand(^(3)IL)triplet state of ethynyl-naphthalimide having a chiral benzylamino moiety.The R/S-PtAu_(2)clusters exhibit significant circularly polarized luminescence(CPL)properties with an asymmetry factor of approximately±1×10^(-3).Organic light-emitting diodes(OLEDs)based on chiral PtAu_(2)clusters demonstrate circularly polarized electroluminescence(CPEL)performance with an asymmetry factor of approximately±7×10^(-4)and an external quantum efficiency(EQE)of 13.7%.The devices exhibit narrow-band red emission and high color purity with CIE 1931 coordinates of(0.68,0.32)and a full width at half maximum(FWHM)of 29 nm.Both circular dichroism(CD)and CPL studies demonstrate the excellent chiral absorption and emission characteristics of trinuclear cluster enantiomers in the ground state as well as in the excited state.
基金supported by the National Natural Science Foundation of China(grant nos.21971006 and 22131003).
文摘Combining spin crossover(SCO)and fluorescence properties could respond to multiple physical stimulus and is meaningful for the development of switches and imaging tools.In this work,we present a new family of neutral mononuclear iron(Ⅱ)complexes,denoted as Fe(L^(1-3))_(2) and Fe(L^(3))_(2)·CH_(2)Cl_(2) with N_(4)O_(2) donor sets.These complexes were synthesized employing a series of tridentate Schiff base ligands,which contain an ethynyl group(HL^(1-3)=3-ethynyl-N′-((4-methylpyridin-2-yl)methylene)benzohydrazide(4MePAH-3EyBHZ,HL^(1)),3-ethynyl-N′-((4-methoxylpyridin-2-yl)methylene)benzohydrazide(4OMe-PAH-3EyBHZ,HL^(2)),3-ethynyl-N′-((5-methylpyridin-2-yl)methylene)benzohydrazide(5MePAH-3EyBHZ,HL^(3))).Variable-temperature magnetic susceptibility measurements revealed that Fe(L^(1))_(2) exhibits an abrupt and complete SCO with characteristic temperature T_(1/2↓)=176 K and T_(1/2↑)=178 K;Fe(L^(2))_(2) exhibits an abrupt and complete SCO with T_(1/2↓)=214 K and T_(1/2↑)=219 K;Fe(L^(3))_(2) exhibits an abrupt and complete SCO with T_(1/2↓)=218 K and T_(1/2↑)=226 K.The partial conformational inversion is observed between the high spin and low spin state of Fe(L^(2))_(2) evidenced by the variable-temperature single-crystal X-ray diffraction analysis.An unusual increase of emission intensity was observed in the fluorescence spectra of Fe(L^(1))_(2) and Fe(L^(2))_(2) during the heating SCO process.These findings are both valuable in the study of spin-fluorescence interaction and synthesis of new multifunctional SCO complexes.
