Novel diarylethene derivatives: N-substituted-3,4-bisheteroaryl-2,5-dihydropyrroleswere synthesized through Mcmurry couple reaction with high yields. The photochromic propertiesand UV-Vis absorption spectra were studi...Novel diarylethene derivatives: N-substituted-3,4-bisheteroaryl-2,5-dihydropyrroleswere synthesized through Mcmurry couple reaction with high yields. The photochromic propertiesand UV-Vis absorption spectra were studied. The maximal absorptions of their close forms werearound at 406 nm or 446 nm, which related mainly with heteroaryl groups but not with substitutedgroups at nitrogen atom of dihydropyrrole. The absorption of their colored form could be matchedwith blue light laser.展开更多
Dynamic chiral materials with noncontactable,lightactivated,and reversible features have attracted considerable attention in photoprogrammable liquid crystals and chiral optoelectronic devices.However,most attempts to...Dynamic chiral materials with noncontactable,lightactivated,and reversible features have attracted considerable attention in photoprogrammable liquid crystals and chiral optoelectronic devices.However,most attempts to construct three-dimensional(3D)supramolecular chiral nanocages are limited to using nonresponsive chiral building blocks,which often results in the formation of architectures in shortage of tunable capacity,especially for the desirable dynamic,photoresponsive,and reversible chirality modulation.Here we report the construction of the first photoswitchable intrinsic chiral metallacages,(P)-and(M)-MOC1 and MOC_(2) based on sterically hindered diarylethene-based subcomponents,thereby achieving the unique light-driven reversible enantiospecific transformation between axial helicity and central asymmetry in 3D cages.Given the increasing cage tension during cyclization,it can be explored as a chiral encapsulant in nanocavity windows while possessing prominent enantioselectivity toward a pair of chiral camphor sulfonate vips.This work opens a new avenue to construct the unprecedented light-activated intrinsic chiral metallacages,aiming at their potential applications for chiral recognition,separation,and asymmetric catalysis.展开更多
Two novel isomeric photochromic diarylethenes with an indene bridging unit have been prepared by a simple and efficient one-step synthesis method. Their properties, including photochromic behavior, fluorescent propert...Two novel isomeric photochromic diarylethenes with an indene bridging unit have been prepared by a simple and efficient one-step synthesis method. Their properties, including photochromic behavior, fluorescent properties and fatigue resistance, have been investigated. These two isomeric compounds showed photochromic back-and-forth reactions with ultraviolet and visible light both in solution and in PMMA film. Their ring-open forms exhibited appreciable fluorescence, which was quenched by the ring-closed forms. All results indicated that diarylethenes derivatives with indene-aryl bridges exhibited rather high fatigue resistance and good thermally irreversible photochromic properties.展开更多
Light-operated excited-state photochemical reactions and the resulting photochromic materials have gained significant attention for their promising technological applications in molecular electronic and photonic devic...Light-operated excited-state photochemical reactions and the resulting photochromic materials have gained significant attention for their promising technological applications in molecular electronic and photonic devices.To obtain photochromic materials(e.g.,diarylethenes)with desired properties,the way to tune energy processes of the excited state is essentially important,from both fundamental and practical viewpoints.The modified diarylethenes mostly focused on structural improvements to achieve efficient photochromism.We report here two new spiro-conjugated indenodiarylethenes(named,SFI-Th and SFI-Sul)with an orthogonally arranged spiroπ-scaffold.The spiro fluorene sterically constrains the free volume of photoactive side aromatic rings,while the spiro-conjugation points toward modulation of the decaying channels of excited-state energy,thus allowing for tuning photochromic performances.These spirodiarylethenes SFI-Th and SFI-Sul are readily accessible with low cost and show distinct photochromic and photoluminescent properties.On one hand,the SFI-Th bearing bisthienyl side rings,is an excellent photochromic switch showing high thermal stability and high fatigue resistance in both solution and amorphous state,likely benefited from steric-induced excited-state energy transfer into reversible photochemical reactions,owing to higherπ-orbital spiro-conjugation between the two molecular halves.On the other hand,the SFI-Sul with bissulfonyl side rings,most notably,displays quantitative photocyclization to yield SFI-Sulc upon excitation.However,the ring-closed SFI-Sulc has an extremely slow photocycloreversion,and meanwhile immediately switches on emissive state with a strong fluorescence(Φf=0.57 in amorphous powder state).We study the modulated roles of spiroπ-scaffold in both cases computationally and experimentally,and attribute the facilitated photochemical reaction to the positively electronic effects of spiro-conjugation,and the photo-responsive radiative transition to the negatively electronic effects of spiro-conjugation,respectively.In all,this work demonstrates that the spiro-conjugation is a new and efficient strategy to deliver excitation energy transfer(EET)for featured photochromic properties,due to its advantage in steric-induced electronic modulation.展开更多
Photon upconversion(UC)is one kind of anti-Stokes shift process,which generally requires a combination of two or more low-energy photons to produce one high-energy photon.However,another interesting anti-Stokes proces...Photon upconversion(UC)is one kind of anti-Stokes shift process,which generally requires a combination of two or more low-energy photons to produce one high-energy photon.However,another interesting anti-Stokes process,namely,single-photon-absorption-based upconversion(SPA-UC),can take place by exciting thermally excited vibrational-rotational energy levels of ground state to the first level of excited state.This phenomenon is less involved in organic systems due to the limitation of appropriate materials.Herein,for the first time,we have demonstrated a series of turn-on mode fluorescent diarylethenes,including Thiophene-and p-alkoxybromo-substituted phenyl-substituted derivatives(DAES and DAEC4),which exhibited SPA-UC phenomenon in the closed-ring state.An anti-Stokes shift of 0.36 eV was observed in these molecules,which was the highest value accessible in such UC systems.A relatively high quantum efficiency(13.5%)was evaluated through a relative method by using methylene blue as a standard.Phonon-assisted or hot band absorption was in charge of the achievement of SPA-UC.Besides,the upconverted emission could be switched on/off by cyclization and cycloreversion reaction,regulated by UV–visible light.Thus,this unique finding of the SPA-UC phenomena in photoswitchable diarylethenes might enrich the development of new molecular engineering strategies for designing photofunctional materials.展开更多
Three new asymmetrical diarylethenes containing an azaindole moiety and a variable heteroaryl ring have been synthesized.Their properties,such as photochromism,fatigue resistance,thermal stability,acidichromism,and fl...Three new asymmetrical diarylethenes containing an azaindole moiety and a variable heteroaryl ring have been synthesized.Their properties,such as photochromism,fatigue resistance,thermal stability,acidichromism,and fluorescence,were systematically investigated to elucidate the effects of aromatic stabilization energies(ASE)of the heteroaryl moieties.The results indicated that thermal stability decreased with the increment of the aromatic stabilization energies of the variable heteroaryl rings in the order of thiazyl〈thienyl〈pyrrolyl.Moreover,the dual switching behaviors of these azaindole-containing diarylethenes were also studied by the stimulation of acid/base and light.Addition of trifluoroacetie acid to the solutions of these diarylethenes resulted in obvious hypochromie shifts,and their N-protonated forms also exhibited favorable photochromism.展开更多
Three new diarylethenes 1--3 combined with quinoline derivatives have been synthesized. Through controlled chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons...Three new diarylethenes 1--3 combined with quinoline derivatives have been synthesized. Through controlled chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons under UV/Vis light irradiation in chloroform solution. It was found that 1--3 had well photoisomerization upon UV/Vis light irradiation in neutral chloroform solution. Addition of acid to the solution of the ring-opening isomers of 1--3 produced 1 oa--3oa, which performed reversible photochromic behavior under UV/Vis light irradiation and reversed back to 1--3 under neutralizing with adding lewis base. However, addtion of base to neutral soluton of the ring-opening isomers of 1--3 produced lob--3ob, which could not change to the deprotonated ring-closing isomers under UV light irradiation.展开更多
The development of multi-stimuli-responsive luminescent system to address emerging demands is essential in anti-counterfeiting field.Herein,a photoswitchable system was reported,which was constructed from photoacid su...The development of multi-stimuli-responsive luminescent system to address emerging demands is essential in anti-counterfeiting field.Herein,a photoswitchable system was reported,which was constructed from photoacid sulfonato-merocyanine(MEH-D)serving as H+donor and diarylethene derivative(DAEA1)as acceptor.After capturing 2 equiv.HCl,the obtained fluorescent molecule DAE-A1-H showed solvatochromic property.Further on,benefiting from that MEH-D released protons and became a ring-closed isomer spiropyran(SP-D)under 440 nm irradiation,DAE-A1 was protonated,turning on fluorescence effect was realized in DAE-A1/MEH-D.In dark,a photo-activated reversible process was realized with SPD changed to MEH-D in situ system.In addition,the OF-DAE-A1-H/SP-D could efficiently and reversibly switch on/off its luminescence upon irradiation by UV–vis light.Significantly,the multi-stimuli-responsive system was successfully applied in logic gate and fluorescence ink,making it an efficient strategy for information encryption and decryption with higher security requirements.展开更多
A new family of photochromic diarylethene compounds, 1-（2-methyl-5-formyl-3- thienyl）-2-（2-methoxylphenyl）perfluorocyclopentene （1o） having an unsymmetrically substituted hexafluorocyclopentene unit, was synthes...A new family of photochromic diarylethene compounds, 1-（2-methyl-5-formyl-3- thienyl）-2-（2-methoxylphenyl）perfluorocyclopentene （1o） having an unsymmetrically substituted hexafluorocyclopentene unit, was synthesized and its structure was determined. The crystal belongs to the monoclinic system, space group P21/c with a = 15.4866（5）, b = 9.0744（9）, c = 12.6906（3）, β = 90.1480（10）°, Z = 4, V = 1783.4（3）3, Dc = 1.513 mg/m3, μ = 0.25, F（000） = 824, the final R = 0.0579 and wR = 0.1566 for 2584 observed reflections （I 2σ（I））. Interestingly, a colorless compound 1o undergoes photocyclization upon irradiation of UV light to give the blue isomer diarylethene. Upon irradiation with visible light with wavelength greater than 510 nm, the blue compound can return to its initial colorless state.展开更多
The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeit...The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeiting. However, to achieve both excellent photoresponsive performance and bright luminescence in solid state remains challenge. Herein, we integrate a novel photochromic fluorophore YL into flexible polymer chains, thereby enabling the resultant polymer PYL with reversible photoisomerization upon aggregation. Remarkably, the polymer PYL possesses excellent photochromic properties and aggregationinduced emission(AIE) activity, which can be attributed to the photoactive YL moiety. Upon light exposure, its film exhibits reversibly off-to-on fluorescent modulation with quick response, high emission efficiency and signal contrast, sharply different from the weak emission in solution. The novel photoresponsive AIE polymer with invisible/visible color and fluorescence transformation allows for advanced anti-counterfeiting applications. This work provides an efficient platform for constructing solid-state photocontrollable luminescent materials.展开更多
In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corres...In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corresponding variation in color,chemical/physical properties,photochromic molecules have been applied in sensors,photo-switches and memories.Incorporation of photochromic molecules to blend in the device functional layers or to modify the interfaces of OFETs is common way to build photo-transistors.In this review,we focus on the recent advantages on the study of photoresponsive transistors involving one of three typical photochromic compounds spiropyran,diarylethene and azobenzene.Three main strategies are demonstrated in detail.Firstly,photochromic molecules are doped in active layers or combined with semiconductor structure thus forming photoreversible active layers.Secondly,the modification of dielectric layer/active layer interface is mainly carried out by bilayer dielectric.Thirdly,the photo-isomerization of self-assembled monolayer（SAM） on the electrode/active layer interface can reversibly modulate the work functions and charge injection barrier,result in bifunctional OFETs.All in all,the combination of photochromic molecules and OFETs is an efficient way for the fabrication of organic photoelectric devices.Photoresponsive transistors consisted of photochromic molecules are potential candidate for real applications in the future.展开更多
A new family of photochromic diarylethene compounds, 1-（2-cyano-l,5-dimethyl- 4-pyrryl）-2-[2-methyl-5-（3-pyridyl）-3-thienyl]perfluorocyclopentene （lo） having an unsymmetrical pyrryl and thienyl substituted hexaf...A new family of photochromic diarylethene compounds, 1-（2-cyano-l,5-dimethyl- 4-pyrryl）-2-[2-methyl-5-（3-pyridyl）-3-thienyl]perfluorocyclopentene （lo） having an unsymmetrical pyrryl and thienyl substituted hexafluorocyclopentene unit, was synthesized and its structure was determined by X-ray analysis. The crystal belongs to triclinic system, space group PI with a = 8.897（7）, b = 10.139（8）, c = 12.361（9） A, α = 85.222（7）, ρ = 75.439（7）, γ = 78.736（8）°, Z = 2, V= 1057.8（14） A3, D,.= 1.468 mg/m3, p = 0.220 mm-1, F（000） = 476, the final R = 0.0608 and wR = 0.1754 for 3199 observed reflections （1 〉20（/））. Interestingly, compound 1 exhibits good photochromic properties with alternate irradiation of UV light and visible light （〉 510 nm） to form two photoisomers in hexane solution and crystal phase.展开更多
A new photochromic diarylethene, [1-（2-methyl-5-（4-cyanophenyl）-3-thienyl-2- （2-methyl-5-phenyl-3-thienyl）]perfluorocyclopentene （lo, C28H17F6NS2）, was synthesized and its structure was determined by single-cry...A new photochromic diarylethene, [1-（2-methyl-5-（4-cyanophenyl）-3-thienyl-2- （2-methyl-5-phenyl-3-thienyl）]perfluorocyclopentene （lo, C28H17F6NS2）, was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its crystal belongs to the monoclinic system, space group P21/c with a = 24.1381（5）, b = 9.3834（6）, c = 11.1073（8）, fl = 94.477（4）°, Z = 4, V= 2508.1（3） A3, Dc = 1.445 mg/m3, μ = 0.275, F（000） = 1112, the final R = 0.0482 and wR = 0.1429 for 5834 observed reflections （I 〉 2σ（I））. Further study demonstrated the diarylethene underwent reversible photochromism, changing between colorless and blue in hexane solution, crystalline phase and PMMA films, respectively.展开更多
The photochromic title compound,C_（26）H_（18）F_6N_2OS_2,contains a 2,5-dimethylthiophene ring and a N-formyl aminoquinolinyl thiophene ring on the C=C double bond of the cyclopentene ring.The dihedral angles betwee...The photochromic title compound,C_（26）H_（18）F_6N_2OS_2,contains a 2,5-dimethylthiophene ring and a N-formyl aminoquinolinyl thiophene ring on the C=C double bond of the cyclopentene ring.The dihedral angles between the cyclopentene and attached N-formyl aminoquinolinyl thiophene ring and 2,5-dimethylthiophene ring are 63.0° and 137.1°,respectively.The dihedral angle between the thiophene ring and the adjacent aminoquinoline ring is 5.7°.The molecule adopts an antiparallel conformation,with a distance between the two photoreactive C atoms of 3.763 ？.In addition,the absorption and fluorescence spectral changes were measured in acetonitile and solid at room temperature,and the result showed that the title compound could undergo photochromic reaction in both states.展开更多
Tetraphenylethene(TPE),a star building block with promising aggregationinduced emission,has received much interest.Given that its intramolecular Woodward-Hoffmann cyclic intermediate instantaneously converts back to t...Tetraphenylethene(TPE),a star building block with promising aggregationinduced emission,has received much interest.Given that its intramolecular Woodward-Hoffmann cyclic intermediate instantaneously converts back to the original state within several picoseconds,the essentially photochromic characteristic of TPE is little investigated.Achieving a visible photocyclization of TPE is still an unsolved issue and considered as the bottleneck in the further advancement of applications.We report a strategy of attaching carbonate ester onto the TPE skeleton(TPE-4C)to enhance TPE photocyclization stability.As demonstrated,the incorporated cholesteryloxycarbonyloxy substituents in TPE-4C can increase the energy barrier for cycloreversion,thereby exhibiting extremely thermal stability of photocyclic intermediate upon UV irradiation,prolonging its lifetime from 63 picoseconds to 46 s by 7.2×10^(11)-fold.The photoinduced cyclization of TPE-4C could be monitored with naked eyes,and the photocyclization/cycloreversion is achieved by turning on/off UV light along with a relative fatigue resistance.Encapsulation of TPE-4C into the liquid crystal can induce a striking phase transformation(achiral↔chiral),which can be applicable to encode optical information.Employing carbonate ester into the TPE unit plays a vital role in enhancing the unprecedented TPE photocyclization stability,providing a toolbox to allow TPE-based photocyclization to be visually monitored.展开更多
A new photochromic diarylethene, [1-（2-methyl-5-（4-chlorophenyl）-3-thienyl-2-（2- methoxylphenyl）]perfluorocyclopentene （1o, C23HIsC1F6OS） was synthesized and its structure was determined by single-crystal X-ray...A new photochromic diarylethene, [1-（2-methyl-5-（4-chlorophenyl）-3-thienyl-2-（2- methoxylphenyl）]perfluorocyclopentene （1o, C23HIsC1F6OS） was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group Pi with a = 9.421（1）, b = 10.4664（1）, c = 11.2988（2）, α= 88.014（1）, β= 76.976（1）,γ= 82.319（1）°, Z= 2, V= 1075.7（2） A3, Dc = 1.509 mg/m3, μ= 0.339 mm-1, F（000） = 496, the final R = 0.0353 and wR = 0.0922 for 3303 observed reflections （I 〉 2σ（I））. Further study demonstrated this compound underwent reversible photochromism with high contrast color-switching between colorless and blue in hexane. Upon UV/Vis irradiation, the fluorescence quenching efficiency can be attached to ca. 98% and recover to the initial state which exhibits high contrast fluorescentswitching between ＂on＂ and ＂off＂ states.展开更多
The crystal structure of fused photochromic diarylethene dimer, 1,4-bis-[4-(4-{2-(5-phenyl)-2-methyl-thiophen-3-yl]-3,3,4,4,5,5-hexafluoro-cyclopent-1-enyl}-5-methyl-thiophen-2-yl) buta-1,3-diyne(1 oo, C46 H23 F12 S4)...The crystal structure of fused photochromic diarylethene dimer, 1,4-bis-[4-(4-{2-(5-phenyl)-2-methyl-thiophen-3-yl]-3,3,4,4,5,5-hexafluoro-cyclopent-1-enyl}-5-methyl-thiophen-2-yl) buta-1,3-diyne(1 oo, C46 H23 F12 S4) was determined by single-crystal X-ray diffraction analysis. This crystal belongs to the triclinic system, space group P1 with a = 7.546(3), b = 8.869(3), c = 16.196(5), α = 98.000(4)°, β = 100.803(4)°, γ = 98.449(4)°, Z = 2, V = 1037.6(6) ?~3, Dc = 1.496 mg/m^3, μ = 0.317, F(000) = 474, the final R = 0.0428 and wR = 0.1199 for 4115 observed reflections(I > 2σ(I)). Further study demonstrated this compound underwent reversible photochromism with color-switching between colorlessness and green in crystalline state. Upon 365 nm irradiation, the diarylethene shows one step photochromism to form isomer 1 oc. When irradiated with 312 nm, the stepwise photocyclization reactions occurred in diarylethene dimer through the line of 1 oo to 1 oc to 1 cc.展开更多
The title compound cis-1,2-dicyano-1,2-bis（2-methyl-4-bromo-3-thienyl）ethane has been synthesized and structurally characterized by X-ray single-crystal diffraction method. Crystal data： triclinic, space group P1^1...The title compound cis-1,2-dicyano-1,2-bis（2-methyl-4-bromo-3-thienyl）ethane has been synthesized and structurally characterized by X-ray single-crystal diffraction method. Crystal data： triclinic, space group P1^1, Z = 2, C14H8Br2N2S2, Mr = 428.16, a = 6.9410（5）, b = 11.0150（9）, c = 11.1760（8） A, α = 70.3390（10）,β = 76.1860（10）, γ = 79.5490（10）°, V= 776.59（10） A^3, Dc = 1.831 g/cm^3, μ（MoKα） = 5.478 mm^-1, F（000） = 416, R = 0.0487 and wR = 0.1453 for 2456 observed reflections with I 〉 2σ（/）. X-ray analysis reveals that the two thiophene rings are significantly twisted with an average dihedral angle of 57.45°. The molecule adopts a photo-active antiparaUel conformation and the distance between the two reactive C atoms of thiophene rings is 3.465（8）A. These structural elements which exhibit a suitable geometry are extensively explored for photochromic behavior in the crystalline state.展开更多
A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spect...A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spectroscopy. Photochromic conversion of Cz-MS was observed and its structural change was confirmed by proton NMR. Switchable absorption and emission phenomena were observed for these molecules. These phenomena were attributed to the reversible photochromic fluorescence resonance energy transfer (pcFRET) process. The design of this novel photochromic system of Py-4MS enables information to be processed in a non-destructive manner. This overcomes the problem of the destructive nature of tracking photochromism using ultraviolet (UV)-vis spectroscopy.展开更多
A new symmetric diarylethene containing cyano group was synthesized and structurally characterized by elemental analysis,IR,1 H NMR and X-ray single-crystal diffraction.It belongs to the monoclinic system,space group ...A new symmetric diarylethene containing cyano group was synthesized and structurally characterized by elemental analysis,IR,1 H NMR and X-ray single-crystal diffraction.It belongs to the monoclinic system,space group C2/c with a = 18.848（6）,b = 8.561（2）,c = 16.875（5） ？,β = 100.398（6）o,V = 1344.6（11） ？~3,Z = 4,μ = 0.262 mm^（-1）,Dc = 1.415 g/cm^3,Mr = 570.56,F（000） = 1160,the final R = 0.0808 and wR = 0.2107 with I 〉 2σ（I）.The two thienyls adopt reactive anti-parallel conformation and the carbon distance of photocyclization is 3.57 ？.The neighboring molecules are stacked closely with C-H…F hydrogen bonding.In addition,the photochromism of the new compound was investigated in solvents with different polarity and PMMA film.The alternative photo-irradiation of 254 nm light and ≥550 visible light can induce the reversible photo-cyclization and photo-reversion with the color interconversion between colorlessness and blue.In THF solution,the λ（max） of diarylethene in PSS in visible band is 585 nm.The diarylethene further reacted with AgBF4 in benzene to give rise to complex 1,which was structurally characterized by elemental analysis,IR,ESI-MS and TG.1 demonstrated reversible photochromism in both solution and PMMA film.The complexation of metal ions with diarylethene leads to a minor red-shift of the λ（max） of 1 in THF in PSS to 590 nm.展开更多
基金We are grateful for financial support of Chinese Key Project(G199933005)NNSFC(60337020 and 20302088).
文摘Novel diarylethene derivatives: N-substituted-3,4-bisheteroaryl-2,5-dihydropyrroleswere synthesized through Mcmurry couple reaction with high yields. The photochromic propertiesand UV-Vis absorption spectra were studied. The maximal absorptions of their close forms werearound at 406 nm or 446 nm, which related mainly with heteroaryl groups but not with substitutedgroups at nitrogen atom of dihydropyrrole. The absorption of their colored form could be matchedwith blue light laser.
基金supported by the National Natural Science Foundation of China(grant nos.92356301,22338006,22305079,and 22108076)Scientific Committee of Shanghai(grant nos.21JC1401700 and 15XD1501400)+2 种基金China Postdoctoral Science Foundation(grant nos.2019M661399,2021M691006,and 2022M721143)Shanghai Sailing Program(grant nos.20YF1410500,22YF1410400,and 23YF1409000)Fundamental Research Funds for the Central Universities(grant no.JKJ01231555).
文摘Dynamic chiral materials with noncontactable,lightactivated,and reversible features have attracted considerable attention in photoprogrammable liquid crystals and chiral optoelectronic devices.However,most attempts to construct three-dimensional(3D)supramolecular chiral nanocages are limited to using nonresponsive chiral building blocks,which often results in the formation of architectures in shortage of tunable capacity,especially for the desirable dynamic,photoresponsive,and reversible chirality modulation.Here we report the construction of the first photoswitchable intrinsic chiral metallacages,(P)-and(M)-MOC1 and MOC_(2) based on sterically hindered diarylethene-based subcomponents,thereby achieving the unique light-driven reversible enantiospecific transformation between axial helicity and central asymmetry in 3D cages.Given the increasing cage tension during cyclization,it can be explored as a chiral encapsulant in nanocavity windows while possessing prominent enantioselectivity toward a pair of chiral camphor sulfonate vips.This work opens a new avenue to construct the unprecedented light-activated intrinsic chiral metallacages,aiming at their potential applications for chiral recognition,separation,and asymmetric catalysis.
文摘Two novel isomeric photochromic diarylethenes with an indene bridging unit have been prepared by a simple and efficient one-step synthesis method. Their properties, including photochromic behavior, fluorescent properties and fatigue resistance, have been investigated. These two isomeric compounds showed photochromic back-and-forth reactions with ultraviolet and visible light both in solution and in PMMA film. Their ring-open forms exhibited appreciable fluorescence, which was quenched by the ring-closed forms. All results indicated that diarylethenes derivatives with indene-aryl bridges exhibited rather high fatigue resistance and good thermally irreversible photochromic properties.
基金This work was supported by the National Natural Science Foundation of China(51922039)Hunan Provincial Natural Science Foundation(2018JJ1008).
文摘Light-operated excited-state photochemical reactions and the resulting photochromic materials have gained significant attention for their promising technological applications in molecular electronic and photonic devices.To obtain photochromic materials(e.g.,diarylethenes)with desired properties,the way to tune energy processes of the excited state is essentially important,from both fundamental and practical viewpoints.The modified diarylethenes mostly focused on structural improvements to achieve efficient photochromism.We report here two new spiro-conjugated indenodiarylethenes(named,SFI-Th and SFI-Sul)with an orthogonally arranged spiroπ-scaffold.The spiro fluorene sterically constrains the free volume of photoactive side aromatic rings,while the spiro-conjugation points toward modulation of the decaying channels of excited-state energy,thus allowing for tuning photochromic performances.These spirodiarylethenes SFI-Th and SFI-Sul are readily accessible with low cost and show distinct photochromic and photoluminescent properties.On one hand,the SFI-Th bearing bisthienyl side rings,is an excellent photochromic switch showing high thermal stability and high fatigue resistance in both solution and amorphous state,likely benefited from steric-induced excited-state energy transfer into reversible photochemical reactions,owing to higherπ-orbital spiro-conjugation between the two molecular halves.On the other hand,the SFI-Sul with bissulfonyl side rings,most notably,displays quantitative photocyclization to yield SFI-Sulc upon excitation.However,the ring-closed SFI-Sulc has an extremely slow photocycloreversion,and meanwhile immediately switches on emissive state with a strong fluorescence(Φf=0.57 in amorphous powder state).We study the modulated roles of spiroπ-scaffold in both cases computationally and experimentally,and attribute the facilitated photochemical reaction to the positively electronic effects of spiro-conjugation,and the photo-responsive radiative transition to the negatively electronic effects of spiro-conjugation,respectively.In all,this work demonstrates that the spiro-conjugation is a new and efficient strategy to deliver excitation energy transfer(EET)for featured photochromic properties,due to its advantage in steric-induced electronic modulation.
基金supported by National Natural Science Foundation of China(51673050,91856115,21905065,and 21907060)the Ministry of Science and Technology of the People’s Republic of China(2017YFA0206600 and 2016YFA0203400)support of China Postdoctoral Science Foundation(BX20180082 and 2019M650603).
文摘Photon upconversion(UC)is one kind of anti-Stokes shift process,which generally requires a combination of two or more low-energy photons to produce one high-energy photon.However,another interesting anti-Stokes process,namely,single-photon-absorption-based upconversion(SPA-UC),can take place by exciting thermally excited vibrational-rotational energy levels of ground state to the first level of excited state.This phenomenon is less involved in organic systems due to the limitation of appropriate materials.Herein,for the first time,we have demonstrated a series of turn-on mode fluorescent diarylethenes,including Thiophene-and p-alkoxybromo-substituted phenyl-substituted derivatives(DAES and DAEC4),which exhibited SPA-UC phenomenon in the closed-ring state.An anti-Stokes shift of 0.36 eV was observed in these molecules,which was the highest value accessible in such UC systems.A relatively high quantum efficiency(13.5%)was evaluated through a relative method by using methylene blue as a standard.Phonon-assisted or hot band absorption was in charge of the achievement of SPA-UC.Besides,the upconverted emission could be switched on/off by cyclization and cycloreversion reaction,regulated by UV–visible light.Thus,this unique finding of the SPA-UC phenomena in photoswitchable diarylethenes might enrich the development of new molecular engineering strategies for designing photofunctional materials.
基金This work was supported by the National Natural Science Foundation of China(51373072,21262015,21162011,21363009)the Project of Jiangxi Advantage Sci-Tech Innovative Team(20142BCB24012)+1 种基金the Science Funds of Natural Science Foundation of Jiangxi Province(20132BAB203005,20142BAB203005)the Project of the Science Funds of Jiangxi Education Office(KJLD12035,GJJ12587,GJJ14592).
文摘Three new asymmetrical diarylethenes containing an azaindole moiety and a variable heteroaryl ring have been synthesized.Their properties,such as photochromism,fatigue resistance,thermal stability,acidichromism,and fluorescence,were systematically investigated to elucidate the effects of aromatic stabilization energies(ASE)of the heteroaryl moieties.The results indicated that thermal stability decreased with the increment of the aromatic stabilization energies of the variable heteroaryl rings in the order of thiazyl〈thienyl〈pyrrolyl.Moreover,the dual switching behaviors of these azaindole-containing diarylethenes were also studied by the stimulation of acid/base and light.Addition of trifluoroacetie acid to the solutions of these diarylethenes resulted in obvious hypochromie shifts,and their N-protonated forms also exhibited favorable photochromism.
基金Supporting information for this article is available on the WWW under http：//dx.doi.org1l 0.1002/cjoc.201200128Ackowlegement This work was supported by the National Basic Research Program of China （973 Program） with No. 2011 CB706900, National Natural Science Foundation of China with No. 50872149 and No. 50502003, Scientific Research Foundation for Returned Scholars within the Ministry of Education of China, and the President Foundation of the Graduate University of Chinese Academy of Sciences.
文摘Three new diarylethenes 1--3 combined with quinoline derivatives have been synthesized. Through controlled chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons under UV/Vis light irradiation in chloroform solution. It was found that 1--3 had well photoisomerization upon UV/Vis light irradiation in neutral chloroform solution. Addition of acid to the solution of the ring-opening isomers of 1--3 produced 1 oa--3oa, which performed reversible photochromic behavior under UV/Vis light irradiation and reversed back to 1--3 under neutralizing with adding lewis base. However, addtion of base to neutral soluton of the ring-opening isomers of 1--3 produced lob--3ob, which could not change to the deprotonated ring-closing isomers under UV light irradiation.
基金financially supported by Natural Science Foundation of Shandong Province(Nos.ZR2022QB061,2022KJ181)National Key R&D Program of China(No.2023YFD1700903)。
文摘The development of multi-stimuli-responsive luminescent system to address emerging demands is essential in anti-counterfeiting field.Herein,a photoswitchable system was reported,which was constructed from photoacid sulfonato-merocyanine(MEH-D)serving as H+donor and diarylethene derivative(DAEA1)as acceptor.After capturing 2 equiv.HCl,the obtained fluorescent molecule DAE-A1-H showed solvatochromic property.Further on,benefiting from that MEH-D released protons and became a ring-closed isomer spiropyran(SP-D)under 440 nm irradiation,DAE-A1 was protonated,turning on fluorescence effect was realized in DAE-A1/MEH-D.In dark,a photo-activated reversible process was realized with SPD changed to MEH-D in situ system.In addition,the OF-DAE-A1-H/SP-D could efficiently and reversibly switch on/off its luminescence upon irradiation by UV–vis light.Significantly,the multi-stimuli-responsive system was successfully applied in logic gate and fluorescence ink,making it an efficient strategy for information encryption and decryption with higher security requirements.
基金Supported by the Project of Natural Science Foundation of Jiangxi Province(2010GZH0040,2010GQH0039)the Project of Jiangxi Youth Scientist,and Science Funds of the Education Office of Jiangxi Province(2010DQ00200,GJJ1067,GJJ11690)
文摘A new family of photochromic diarylethene compounds, 1-（2-methyl-5-formyl-3- thienyl）-2-（2-methoxylphenyl）perfluorocyclopentene （1o） having an unsymmetrically substituted hexafluorocyclopentene unit, was synthesized and its structure was determined. The crystal belongs to the monoclinic system, space group P21/c with a = 15.4866（5）, b = 9.0744（9）, c = 12.6906（3）, β = 90.1480（10）°, Z = 4, V = 1783.4（3）3, Dc = 1.513 mg/m3, μ = 0.25, F（000） = 824, the final R = 0.0579 and wR = 0.1566 for 2584 observed reflections （I 2σ（I））. Interestingly, a colorless compound 1o undergoes photocyclization upon irradiation of UV light to give the blue isomer diarylethene. Upon irradiation with visible light with wavelength greater than 510 nm, the blue compound can return to its initial colorless state.
基金financially supported by the National Natural Science Foundation of China for Science Center Program (No. 21788102)Creative Research Groups (No. 21421004)+4 种基金Key Project (No. 21636002)Shanghai Pujiang Program (No. 20PJ1402900)National key Research and Development Program (No. 2016YFA0200300)Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)Program of Introducing Talents of Discipline to Universities (No. B16017)。
文摘The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeiting. However, to achieve both excellent photoresponsive performance and bright luminescence in solid state remains challenge. Herein, we integrate a novel photochromic fluorophore YL into flexible polymer chains, thereby enabling the resultant polymer PYL with reversible photoisomerization upon aggregation. Remarkably, the polymer PYL possesses excellent photochromic properties and aggregationinduced emission(AIE) activity, which can be attributed to the photoactive YL moiety. Upon light exposure, its film exhibits reversibly off-to-on fluorescent modulation with quick response, high emission efficiency and signal contrast, sharply different from the weak emission in solution. The novel photoresponsive AIE polymer with invisible/visible color and fluorescence transformation allows for advanced anti-counterfeiting applications. This work provides an efficient platform for constructing solid-state photocontrollable luminescent materials.
基金supported financially by the National Natural Science Foundation of China(Nos.21302212 and 21522209)the "Strategic Priority Research Program"(No.XDB12010100)
文摘In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corresponding variation in color,chemical/physical properties,photochromic molecules have been applied in sensors,photo-switches and memories.Incorporation of photochromic molecules to blend in the device functional layers or to modify the interfaces of OFETs is common way to build photo-transistors.In this review,we focus on the recent advantages on the study of photoresponsive transistors involving one of three typical photochromic compounds spiropyran,diarylethene and azobenzene.Three main strategies are demonstrated in detail.Firstly,photochromic molecules are doped in active layers or combined with semiconductor structure thus forming photoreversible active layers.Secondly,the modification of dielectric layer/active layer interface is mainly carried out by bilayer dielectric.Thirdly,the photo-isomerization of self-assembled monolayer（SAM） on the electrode/active layer interface can reversibly modulate the work functions and charge injection barrier,result in bifunctional OFETs.All in all,the combination of photochromic molecules and OFETs is an efficient way for the fabrication of organic photoelectric devices.Photoresponsive transistors consisted of photochromic molecules are potential candidate for real applications in the future.
基金Supported by the NNSFC(21262015,21162011)Science Funds of the Education Office of Jiangxi Province(GJJ11690,GJJ13577)
文摘A new family of photochromic diarylethene compounds, 1-（2-cyano-l,5-dimethyl- 4-pyrryl）-2-[2-methyl-5-（3-pyridyl）-3-thienyl]perfluorocyclopentene （lo） having an unsymmetrical pyrryl and thienyl substituted hexafluorocyclopentene unit, was synthesized and its structure was determined by X-ray analysis. The crystal belongs to triclinic system, space group PI with a = 8.897（7）, b = 10.139（8）, c = 12.361（9） A, α = 85.222（7）, ρ = 75.439（7）, γ = 78.736（8）°, Z = 2, V= 1057.8（14） A3, D,.= 1.468 mg/m3, p = 0.220 mm-1, F（000） = 476, the final R = 0.0608 and wR = 0.1754 for 3199 observed reflections （1 〉20（/））. Interestingly, compound 1 exhibits good photochromic properties with alternate irradiation of UV light and visible light （〉 510 nm） to form two photoisomers in hexane solution and crystal phase.
基金Supported by the National Natural Science Foundation of China(5137307221363009)+3 种基金the Project of Natural Science Foundation of Jiangxi Province(20142BAB203005)the Project of Science Funds of Jiangxi Education Office(KJLD12035GJJ13577)the PhD start-up fund of Jiangxi Science&Technology Normal University
文摘A new photochromic diarylethene, [1-（2-methyl-5-（4-cyanophenyl）-3-thienyl-2- （2-methyl-5-phenyl-3-thienyl）]perfluorocyclopentene （lo, C28H17F6NS2）, was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its crystal belongs to the monoclinic system, space group P21/c with a = 24.1381（5）, b = 9.3834（6）, c = 11.1073（8）, fl = 94.477（4）°, Z = 4, V= 2508.1（3） A3, Dc = 1.445 mg/m3, μ = 0.275, F（000） = 1112, the final R = 0.0482 and wR = 0.1429 for 5834 observed reflections （I 〉 2σ（I））. Further study demonstrated the diarylethene underwent reversible photochromism, changing between colorless and blue in hexane solution, crystalline phase and PMMA films, respectively.
基金Supported by the National Natural Science Foundation of China(51373072,21363009)the Project of Natural Science Foundation of Jiangxi Province(20142BAB203005)+2 种基金the Project of Science Funds of Jiangxi Education Office(KJLD12035)the Young scientist training program of Jiangxi(20153BCB23008)the PhD start-up fund of Jiangxi Science&Technology Normal University
文摘The photochromic title compound,C_（26）H_（18）F_6N_2OS_2,contains a 2,5-dimethylthiophene ring and a N-formyl aminoquinolinyl thiophene ring on the C=C double bond of the cyclopentene ring.The dihedral angles between the cyclopentene and attached N-formyl aminoquinolinyl thiophene ring and 2,5-dimethylthiophene ring are 63.0° and 137.1°,respectively.The dihedral angle between the thiophene ring and the adjacent aminoquinoline ring is 5.7°.The molecule adopts an antiparallel conformation,with a distance between the two photoreactive C atoms of 3.763 ？.In addition,the absorption and fluorescence spectral changes were measured in acetonitile and solid at room temperature,and the result showed that the title compound could undergo photochromic reaction in both states.
基金supported by NSFC/China(21788102,21636002,21622602,21875143,21908146,and 21908060)Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)+3 种基金Innovation Program of Shanghai Municipal Education Commission,Scientific Committee of Shanghai(15XD1501400)Programme of Introducing Talents of Discipline to Universities(B16017)China Postdoctoral Science Foundation(2019M651417)Innovation Research Foundation of Shenzhen(JCYJ20180507182229597).
文摘Tetraphenylethene(TPE),a star building block with promising aggregationinduced emission,has received much interest.Given that its intramolecular Woodward-Hoffmann cyclic intermediate instantaneously converts back to the original state within several picoseconds,the essentially photochromic characteristic of TPE is little investigated.Achieving a visible photocyclization of TPE is still an unsolved issue and considered as the bottleneck in the further advancement of applications.We report a strategy of attaching carbonate ester onto the TPE skeleton(TPE-4C)to enhance TPE photocyclization stability.As demonstrated,the incorporated cholesteryloxycarbonyloxy substituents in TPE-4C can increase the energy barrier for cycloreversion,thereby exhibiting extremely thermal stability of photocyclic intermediate upon UV irradiation,prolonging its lifetime from 63 picoseconds to 46 s by 7.2×10^(11)-fold.The photoinduced cyclization of TPE-4C could be monitored with naked eyes,and the photocyclization/cycloreversion is achieved by turning on/off UV light along with a relative fatigue resistance.Encapsulation of TPE-4C into the liquid crystal can induce a striking phase transformation(achiral↔chiral),which can be applicable to encode optical information.Employing carbonate ester into the TPE unit plays a vital role in enhancing the unprecedented TPE photocyclization stability,providing a toolbox to allow TPE-based photocyclization to be visually monitored.
基金Supported by the National Natural Science Foundation of China(51373072,21363009)the Project of Natural Science Foundation of Jiangxi Province(20142BAB203005)the Program for the Top Young Innovative Talents in University(2013QNBJRC002)
文摘A new photochromic diarylethene, [1-（2-methyl-5-（4-chlorophenyl）-3-thienyl-2-（2- methoxylphenyl）]perfluorocyclopentene （1o, C23HIsC1F6OS） was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group Pi with a = 9.421（1）, b = 10.4664（1）, c = 11.2988（2）, α= 88.014（1）, β= 76.976（1）,γ= 82.319（1）°, Z= 2, V= 1075.7（2） A3, Dc = 1.509 mg/m3, μ= 0.339 mm-1, F（000） = 496, the final R = 0.0353 and wR = 0.0922 for 3303 observed reflections （I 〉 2σ（I））. Further study demonstrated this compound underwent reversible photochromism with high contrast color-switching between colorless and blue in hexane. Upon UV/Vis irradiation, the fluorescence quenching efficiency can be attached to ca. 98% and recover to the initial state which exhibits high contrast fluorescentswitching between ＂on＂ and ＂off＂ states.
基金Supported by the National Natural Science Foundation of China(21701065)"5511" Science and Technology Innovation Talent Project of Jiangxi Province(20165BCB18015)+2 种基金the Project of Natural Science Foundation of Jiangxi Province(20171ACB20025,20171BAB203011)the Project of the Science Funds of Jiangxi Education Office(GJJ170659)the Project of Jiangxi Advantage Sci-Tech Innovative Team(20142BCB24012)
文摘The crystal structure of fused photochromic diarylethene dimer, 1,4-bis-[4-(4-{2-(5-phenyl)-2-methyl-thiophen-3-yl]-3,3,4,4,5,5-hexafluoro-cyclopent-1-enyl}-5-methyl-thiophen-2-yl) buta-1,3-diyne(1 oo, C46 H23 F12 S4) was determined by single-crystal X-ray diffraction analysis. This crystal belongs to the triclinic system, space group P1 with a = 7.546(3), b = 8.869(3), c = 16.196(5), α = 98.000(4)°, β = 100.803(4)°, γ = 98.449(4)°, Z = 2, V = 1037.6(6) ?~3, Dc = 1.496 mg/m^3, μ = 0.317, F(000) = 474, the final R = 0.0428 and wR = 0.1199 for 4115 observed reflections(I > 2σ(I)). Further study demonstrated this compound underwent reversible photochromism with color-switching between colorlessness and green in crystalline state. Upon 365 nm irradiation, the diarylethene shows one step photochromism to form isomer 1 oc. When irradiated with 312 nm, the stepwise photocyclization reactions occurred in diarylethene dimer through the line of 1 oo to 1 oc to 1 cc.
文摘The title compound cis-1,2-dicyano-1,2-bis（2-methyl-4-bromo-3-thienyl）ethane has been synthesized and structurally characterized by X-ray single-crystal diffraction method. Crystal data： triclinic, space group P1^1, Z = 2, C14H8Br2N2S2, Mr = 428.16, a = 6.9410（5）, b = 11.0150（9）, c = 11.1760（8） A, α = 70.3390（10）,β = 76.1860（10）, γ = 79.5490（10）°, V= 776.59（10） A^3, Dc = 1.831 g/cm^3, μ（MoKα） = 5.478 mm^-1, F（000） = 416, R = 0.0487 and wR = 0.1453 for 2456 observed reflections with I 〉 2σ（/）. X-ray analysis reveals that the two thiophene rings are significantly twisted with an average dihedral angle of 57.45°. The molecule adopts a photo-active antiparaUel conformation and the distance between the two reactive C atoms of thiophene rings is 3.465（8）A. These structural elements which exhibit a suitable geometry are extensively explored for photochromic behavior in the crystalline state.
基金Project supported by the National Natural Science Foundation of China (No. 20674070)the Natural Science Foundation of Zhejiang Province (No. R404109), China
文摘A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spectroscopy. Photochromic conversion of Cz-MS was observed and its structural change was confirmed by proton NMR. Switchable absorption and emission phenomena were observed for these molecules. These phenomena were attributed to the reversible photochromic fluorescence resonance energy transfer (pcFRET) process. The design of this novel photochromic system of Py-4MS enables information to be processed in a non-destructive manner. This overcomes the problem of the destructive nature of tracking photochromism using ultraviolet (UV)-vis spectroscopy.
基金supported by the Project Sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars(Yu Zhong)Shaanxi Natural Science Foundation(No.2017JM2021)Scientific Research Program of Xi’an University of Technology(No.2015CX001)
文摘A new symmetric diarylethene containing cyano group was synthesized and structurally characterized by elemental analysis,IR,1 H NMR and X-ray single-crystal diffraction.It belongs to the monoclinic system,space group C2/c with a = 18.848（6）,b = 8.561（2）,c = 16.875（5） ？,β = 100.398（6）o,V = 1344.6（11） ？~3,Z = 4,μ = 0.262 mm^（-1）,Dc = 1.415 g/cm^3,Mr = 570.56,F（000） = 1160,the final R = 0.0808 and wR = 0.2107 with I 〉 2σ（I）.The two thienyls adopt reactive anti-parallel conformation and the carbon distance of photocyclization is 3.57 ？.The neighboring molecules are stacked closely with C-H…F hydrogen bonding.In addition,the photochromism of the new compound was investigated in solvents with different polarity and PMMA film.The alternative photo-irradiation of 254 nm light and ≥550 visible light can induce the reversible photo-cyclization and photo-reversion with the color interconversion between colorlessness and blue.In THF solution,the λ（max） of diarylethene in PSS in visible band is 585 nm.The diarylethene further reacted with AgBF4 in benzene to give rise to complex 1,which was structurally characterized by elemental analysis,IR,ESI-MS and TG.1 demonstrated reversible photochromism in both solution and PMMA film.The complexation of metal ions with diarylethene leads to a minor red-shift of the λ（max） of 1 in THF in PSS to 590 nm.
