CN110305105A - Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application - Google Patents

Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application Download PDF

Info

Publication number
CN110305105A
CN110305105A CN201910682255.3A CN201910682255A CN110305105A CN 110305105 A CN110305105 A CN 110305105A CN 201910682255 A CN201910682255 A CN 201910682255A CN 110305105 A CN110305105 A CN 110305105A
Authority
CN
China
Prior art keywords
compound
formula
aldehyde
molecular skeleton
functionsization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910682255.3A
Other languages
Chinese (zh)
Inventor
卢志强
李自永
秦铭
杜晓彤
王宇晴
王墨
李利兵
张振奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Luoyang Normal University
Original Assignee
Luoyang Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Luoyang Normal University filed Critical Luoyang Normal University
Priority to CN201910682255.3A priority Critical patent/CN110305105A/en
Publication of CN110305105A publication Critical patent/CN110305105A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/10—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

It is conjugated the present invention relates to aldehyde functionsization di-thiofuran ethylene and extends versatility molecular skeleton compound and its preparation method and application, electron-withdrawing group is introduced into Dithiophene molecular skeleton two sides, realize the building of (receptor-di-thiofuran ethylene-receptor) type actinic material molecular skeleton, wherein the presence of drawing electron group can further decrease the energy differences between the frontier orbit of di-thiofuran ethylene ring-opened monomer in long conjugated system, and make the extinction wavelength further occurrence red shift of molecule, the photochromic material has good photochromic properties, good anti-fatigue performance is all had under ultraviolet or visible light irradiation.

Description

Aldehyde functionsization di-thiofuran ethylene conjugation extend versatility molecular skeleton compound and Preparation method and application
Technical field
The present invention relates to photochromic material technical fields, and in particular to aldehyde functionsization di-thiofuran ethylene conjugation extends Versatility molecular skeleton compound and its preparation method and application.
Background technique
In recent years, the photochromic material of the molecular skeletons such as azobenzene, spiro-pyrans, diarylethene, because it is in molecule device In part and optical storage system application and receive significant attention.Wherein, di-thiofuran ethylene is because it is with good thermal stability, fast The features such as the response of fast optical signal, the regulation of invertibity optics and enhanced ageing resistance, by field researcher it is extensive Concern.Meanwhile nearly red place's photochromic material, because having potential photoelectron performance and photopharmacology performance, correlative study is It is inquired into as the hot spot of a duration, and widely.Under normal circumstances, the method for near-infrared photochromic material is designed There are many.Wherein, by extending the conjugated backbone of intramolecular, the energy of the HOMO-LUMO interorbital of open loop body skeleton is effectively reduced Measuring difference is a kind of highly important MOLECULE DESIGN thinking.At the same time, some alternative thinkings are also constantly used for close red The MOLECULE DESIGN of outer photochromic material.For example, in the molecule introduce triplet state photosensitive structure, be added up-conversion nanoparticles, Be loaded into Multiphoton Absorbtion structure and introduce donor-π-acceptor molecule system etc..However, these alternative methods are different Generate to degree that circulation light quantum efficiency is weak and light sensitivity structure be to the sensibility feature of triplet oxygen, and by introducing on The method for converting nano-carrier or multi-photon channel is then extremely complex in design, and its result is not easy to control.
Summary of the invention
The present invention in order to overcome the above-mentioned deficiencies of the prior art, provides a kind of aldehyde functionsization di-thiofuran ethylene conjugation and prolongs Stretch versatility molecular skeleton compound and its preparation method and application.
The technical scheme adopted by the invention is that: aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton Compound is compound shown in formula I and II:
Wherein, the integer that n is >=0, R=X (F, Cl, Br, I) and Ar.
Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound, is compound shown below:
Aldehyde functionsization di-thiofuran ethylene conjugation extends the preparation method of versatility molecular skeleton compound:
Using compound shown in formula III as starting material, obtained type I compound (n=0) by witting reaction synthesis, I chemical combination of formula Object (n=0) obtains type I compound (n=1) by witting reaction synthesis, and type I compound (n=1) is reacted by witting Synthesis obtains type I compound (n=2), and so on, obtain type I compound (n is >=0 integer)；
Or, obtaining II compound of formula (n=0), formula by witting reaction synthesis using compound shown in formula IV as starting material II compound (n=0) obtains II compound of formula (n=1) by witting reaction synthesis, and II compound of formula (n=1) passes through Witting reaction synthesis obtains II compound of formula (n=2), and so on, obtain II compound of formula (n is >=0 integer)；
。
Wherein, the preparation method of type I compound (n=0) specifically: (1,3- dioxin -2- ethyl is added in anhydrous THF Methyl)-triphenylphosphinebromide and NaOMe, it is added the THF solution of III compound of formula under nitrogen protection, mixture back flow reaction, instead It is cooled to room temperature after answering, through extraction, drying and filtering and concentrating, obtained solid is handled in water with 10% HCl, at room temperature Then stirring is added 2M NaOH and carries out neutralization reaction, reaction mixture through extraction, drying, filtering and concentrating and column chromatography for separation, Obtain type I compound (n=0).
Wherein, the preparation method of II compound of formula (n=0) specifically: (1,3- dioxin -2- second is added in anhydrous THF Ylmethyl)-triphenylphosphinebromide and NaOMe, it is added the THF solution of IV compound of formula under nitrogen protection, mixture back flow reaction, It is cooled to room temperature after reaction, through extraction, drying and filtering and concentrating, obtained solid is dissolved in THF, with 10% HCl in water Middle processing, is stirred at room temperature, and 2M NaOH is then added and carries out neutralization reaction, reaction mixture is through extraction, drying, filtering and concentrating And column chromatography for separation, obtain II compound of formula (n=0).
Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound in the photochromic material of near-infrared Application on material shows good photochromic properties under ultraviolet light, and has good anti-aging property.
Beneficial effect
One, electron-withdrawing group is introduced into di-thiofuran ethylene molecular skeleton two sides by the present invention, realize (receptor-di-thiofuran ethylene-by Body) type actinic material molecular skeleton building, wherein the presence of drawing electron group can further decrease in long conjugated system Energy differences between the frontier orbit of di-thiofuran ethylene open loop body, and make the extinction wavelength further occurrence red shift of molecule, the light It causes off-color material that there are good photochromic properties, all has good fatigue resistance under the penetrating that ultraviolet or visible light shines Energy；
Two, the aldehyde groups in the molecular skeleton of material of the present invention act not only as electron-withdrawing group, to the optical of molecule It can have an impact；Meanwhile the functional group classical as one, aldehyde radical can pass through the methods of oxidation, reduction, condensation realization pair The directed modification of molecular structure, to be possibly realized to the multiple regulation of the functionality of photochromic molecules skeleton.
Detailed description of the invention
Fig. 1 be situation of change of the 1b absorbing wavelength in toluene solution, illustration be it is light-initiated under the conditions of correspond to the macro of molecule See figure；
Fig. 2 is situation of change of the 1c absorbing wavelength in toluene solution, illustration be it is light-initiated under the conditions of correspond to the macrograph of molecule；
Fig. 3 is situation of change of the 2b absorbing wavelength in toluene solution, illustration be it is light-initiated under the conditions of correspond to the macrograph of molecule；
Fig. 4 is situation of change of the 2c absorbing wavelength in toluene solution, illustration be it is light-initiated under the conditions of correspond to the macrograph of molecule；
Fig. 5 is 1b, 1c, 2b and 2c under the conditions of 365 nm ultraviolet lights under toluene middle ring enclosed isomers maximum absorption wavelength Photoresponse rate；
Fig. 6 is the optimization ground state of resulting 1b and 1c under the conditions of B3LYP/6-31G* level based on 09 program of Gaussian Conformational map；
Fig. 7 is the resulting front the 1b and 1c molecule rail under the conditions of B3LYP/6-31G* level based on 09 program of Gaussian Road distribution map；
Fig. 8 is anti-fatigue performance figure of the 1b in toluene under ultraviolet light and visible light alternating irradiation；
Fig. 9 is anti-fatigue performance figure of the 1c in toluene under ultraviolet light and visible light alternating irradiation；
Figure 10 is anti-fatigue performance figure of the 2b in toluene under ultraviolet light and visible light alternating irradiation；
Figure 11 is anti-fatigue performance figure of the 2c in toluene under ultraviolet light and visible light alternating irradiation；
Figure 12 is the optimization ground state of resulting 2b and 2c under the conditions of B3LYP/6-31G* level based on 09 program of Gaussian Conformational map
Figure 13 is the resulting forward position the 2b and 2c molecule rail under the conditions of B3LYP/6-31G* level based on 09 program of Gaussian Road distribution map.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1
The preparation method of type I compound (n=0) specifically: (1,3- dioxin -2- ethyl is added in anhydrous THF (10 mL) Methyl)-triphenylphosphinebromide (1.72 g, 4.0 mmol) and NaOMe (0.74 mL, 5.4 M methanol solution, 4.0 mmol), The THF(0.1 M of III compound of formula (316 mg, 1.0 mmol) is added under nitrogen protection) solution.Mixture flow back 12 h, it is cold But it to room temperature, is extracted with EtOAc (3 × 30 mL).It is organic with MgSO4On dry, filter concentration.Solid is existed with 10% HCl (10 mL) is handled in water, is stirred 2 hours at room temperature, reaction mixture is neutralized by 2M NaOH.Mixture with EtOAc (3 × 30 mL) extraction, MgSO4Upper drying is filtered under diminished pressure concentration.Column chromatography for separation (silica gel: 200-300, PE:EA=9: 1) faint yellow solid (Yield:78%), is obtained1H NMR (400 MHz, CDCl3) δ 9.57 (d, J = 7.7 Hz, 2H), 7.42 (d, J = 15.5 Hz, 2H), 7.02 (s, 2H), 6.35 (dd, J = 15.5, 7.7 Hz, 2H), 2.80 (t, J = 7.5 Hz, 4H), 2.13- 2.06 (m, 2H), 2.02 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 192.83, 144.45, 141.31, 137.37, 135.69, 134.90, 133.63, 126.57, 38.50, 23.03, 15.10. HRMS (ESI-TOF) m/z: [M + H]+ Calcd forC21H21O2S2369.0983; Found 369.0961。
Embodiment 2
The preparation method of type I compound (n=1) specifically: (1,3- dioxin -2- ethyl is added in anhydrous THF (10 mL) Methyl) and-triphenylphosphinebromide (1.72 g, 4.0 mmol) and NaOMe (0.74 mL, 5.4 M methanol solutions, 4.0 Mmol), the THF(0.1 M of type I compound (n=0) (316 mg, 1.0 mmol) is added under nitrogen protection) solution.Mixture Flow back 12 h, is cooled to room temperature, and is extracted with EtOAc (3 × 30 mL).It is organic with MgSO4On dry, filter concentration.Solid It is handled, is stirred 2 hours at room temperature, reaction mixture is neutralized by 2M NaOH in water (10 mL) with 10% HCl.Mixture is used EtOAc (3 × 30 mL) extraction, MgSO4Upper drying is filtered under diminished pressure concentration.Column chromatography for separation (silica gel: 200-300, PE: EA=9:1), obtain yellow solid (Yield:61 %)1H NMR (400 MHz, CDCl3) δ 9.56 (d, J = 8.0 Hz, 2H), 7.15 (dd, J = 15.1, 11.2 Hz, 2H), 6.76 (s, 2H), 6.80- 6.70 (m, 2H), 6.55 - 6.45 (m, 2H), 6.16 (dd, J = 15.1, 7.9 Hz, 2H), 2.77 (t, J = 7.4 Hz, 4H), 2.07- 2.02 (m, 2H), 1.96 (s, 6H).13C NMR (100 MHz, CDCl3) δ 193.53, 151.87, 142.54, 137.99, 136.83, 134.68, 131.19, 130.84, 129.45, 126.39, 38.50, 23.04, 14.90. HRMS (ESI-TOF) m/z: [M +H]+ Calcd forC25H25O2S2421.1296; Found 421.1293。
Embodiment 3
The preparation method of II compound of formula (n=0) specifically: (1,3- dioxin -2- ethyl is added in anhydrous THF (10 mL) Methyl) and-triphenylphosphinebromide (1.72 g, 4.0 mmol) and NaOMe (0.74 mL, 5.4 M methanol solutions, 4.0 Mmol THF (0.2M) solution of IV compound of formula (644 mg, 2.0 mmol), solution are added under nitrogen protection for) solution.Institute It obtains mixture to flow back 8 hours, be cooled to room temperature, extracted with EtOAc (3 × 30 mL).Combined organic layers are with MgSO4It is dry, Filtering and concentrating.Solid is dissolved in THF (10 mL), is handled in water (10 mL) with 10% HCl.It stirs 2 hours, uses at room temperature 2M sodium hydroxide neutralization reaction.Mixture, organic layer MgSO are extracted with EtOAc (3 × 30 mL)4Dry, filter concentration.Column Chromatography (silica gel: 200-300, PE:EA=9:1), obtains faint yellow solid (Yield:81%)1H NMR (400 MHz, CDCl3) δ 9.58 (d, J = 7.7 Hz, 1H), 7.43 (d, J = 15.5 Hz, 1H), 7.02 (s, 1H), 6.59 (s, 1H), 6.35 (dd, J = 15.5, 7.7 Hz, 1H), 2.80- 2.73 (m, 4H), 2.10- 2.03 (m, 2H), 2.05 (s, 3H), 1.87 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 192.70, 144.49, 141.22, 137.35, 135.29, 135.08, 134.63, 134.05, 133.70, 133.26, 126.56, 126.22, 125.43, 38.33, 38.27, 22.84, 14.96, 14.11. HRMS (ESI- TOF) m/z: [M + H]+ Calcd forC18H18ClOS2 349.0488; Found 349.0480。
Embodiment 4
The preparation method of II compound of formula (n=1) specifically: (1,3- dioxin -2- ethyl is added in anhydrous THF (10 mL) Methyl) and-triphenylphosphinebromide (1.72 g, 4.0 mmol) and NaOMe (0.74 mL, 5.4 M methanol solutions, 4.0 Mmol THF (0.2 M) solution of II compound of formula (n=0) (644 mg, 2.0 mmol) is added under nitrogen protection for) solution, molten Liquid.Gained mixture flows back 8 hours, is cooled to room temperature, and is extracted with EtOAc (3 × 30 mL).Combined organic layers are with MgSO4 Dry, filter concentration.Solid is dissolved in THF (10 mL), is handled in water (10 mL) with 10% HCl.Stirring 2 is small at room temperature When, with 2 M sodium hydroxide neutralization reactions.Mixture, organic layer MgSO are extracted with EtOAc (3 × 30 mL)4It dries, filters Concentration.Column chromatography for separation (silica gel: 200-300, PE:EA=9:1) obtains faint yellow solid (Yield:74 %) 1H NMR (400 MHz, CDCl3) δ 9.57 (d, J = 8.0 Hz, 1H), 7.17 (dd, J = 14.9, 11.4 Hz, 1H), 6.98 (d, J = 15.1 Hz, 1H), 6.84 (s, 1H), 6.69 – 6.60 (m, 1H), 6.58 (s, 1H), 6.19 (dd, J = 15.0, 7.8 Hz, 1H), 2.75 (dd, J = 15.0, 7.5 Hz, 4H), 2.05 (dd, J = 14.8, 7.5 Hz, 2H), 2.01 (s, 3H), 1.87 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 193.52, 151.98, 138.58, 137.20, 136.97, 135.10, 134.95, 134.81, 134.55, 133.41, 131.21, 130.69, 126.81, 125.43, 124.62, 38.47, 38.44, 23.00, 14.98, 14.28. HRMS (ESI-TOF) m/z: [M +H]+ Calcd forC20H20ClOS2375.0644; Found 375.0630。
Photochromic Performance Test
It should be noted that 1b, 1c, 2b, 2c in Fig. 1-13 respectively represent following compound:
Its structure is characterized and confirmed by nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra and high resolution mass spectrum.From them 's1It can be found that the bimodal coupling constant of vinyl hydrogen is 15.5 Hz in HNMR spectrogram, this shows that conjugated double bond is in instead Formula configuration.
Compound 1b, 1c, 2b, 2c reversible photochemical reaction diagram
It is tested for the photochromic behavior of compound 1b, 1c, 2b, 2c in toluene.As shown in Figure 1, in toluene, The maximum absorption band that isomers 1b (o) is is (ε=1.68 × 10 308nm4m-1cm-1) and (ε=1.67 × 10 352nm4m-1cm-1), this difference is the result of π-π * transition in molecule.After with the irradiation of 365nm ultraviolet light after this solution, a new absorption band In (ε=1.29 × 10 622nm4M-1cm-1) one new absorption peak of position appearance, meanwhile, the color of solution becomes blue by colourless Color, compound are also converted to closed loop isomers 1b (c), meanwhile, occur apparent sosbestic point at 376nm, by this point, quilt It is completely converted into photocyclization product 1b (c).Under visible light (> 402nm) irradiation, blue cyclization isomers 1b (c) carries out ring Reduction reaction forms initial colourless open loop isomers.It is both, by the open loop and closed loop of light irradiation compound 1b, Ke Yiguan Observe good ability of reverse photochromism behavior (Fig. 8).Quantum efficiency of the cyclisation and open loop isomers of 1b in toluene be respectively 0.59(φo-c) and 0.0085 (φc-o)。
Similarly, 1c, 2b are similar (as shown in Fig. 2-4 and 9-11) in the photochromic behavior of toluene solution with 2c.Four classes Photoresponse rate sequence of the molecule in toluene is 1b > 2b > 1c > 2c (Fig. 5), it means that 1b and 2b ratio has longer conjugation The analog 1c and 2c of system can more effectively reach photostationary state.Their photochromic parameter shows the length pair of conjugated chain Their photochromic properties have a significant impact, as molar extinction coefficient, absorption maximum, cyclisation and open loop body quantum yield Deng.The molar absorption coefficient of 1c and 2c open loop isomers is greater than 1b and 2b.The maximum of 1c open loop and closed loop isomers in toluene There is apparent red shift compared with molecule 1b corresponds to situation in absorbing wavelength, this is attributed to the increase of 1c conjugated structure.1b,1c,2b With the closed loop quantum efficiency (φ of 2c moleculeo-c) to be much higher than respective open loop isomers quantum efficiency.Therefore, 1b and 2b ratio corresponds to Analog 1c and 2c quantum efficiency it is high, therefore, the former shows better photochromic properties.
In order to be more clearly understood that the relationship between the electronic property of 1b, 1c, 2b and 2c and photoreactivity, patent utilize close Degree Functional Theory (DFT) calculates their electron density and ground state geometry (09 B3LYP/6-31G* of Gaussian Level), as shown in Fig. 6 and Figure 12, the open loop isomers of 1b, 1c, 2b and 2c are in classical non-parallel conformations.In addition, such as Fig. 7 And energy 1 b (o), 1 c (o), 2 b (o) and 2 c (o) of Figure 13, HOMO track are mainly distributed on di-thiofuran ethylene list Member, however, due to the sucting electronic effect of aldehyde radical, so that their LUMO orbital energy is mainly distributed on acyl moieties, this confirmation Receptor-di-thiofuran ethylene-receptor structure feature of 1 b and 1c molecular structure type.For cyclic isomers, they The skeleton structure for the conjugation for being similar to plane is shown, corresponding HOMO orbital energy is also mainly distributed on the double thiophene knots in center On structure, LUMO energy is then almost distributed on entire molecule.Molecule 1 b (c), c (c), 2b (c) and 2c (c) are the same as right The open loop isomers energy level of frontier orbital difference (3.27-3.69 ev) answered is compared, and shows one compared with thin pillar (1.83- 2.35 ev), this is because the extension of pi-conjugated system causes in molecule.In addition, the energy difference of each molecule is away from pi-conjugated system Extend and increase accordingly (for example, 1c (o), 3.27 ev, 1b (o), 3.68 ev；1c (c) 1.83 ev, 1b (c), 2.02 Ev, this is consistent with the experimental result of the intermolecular corresponding Relation Between Redshift of 1b with 1c.Therefore, it is photochromic to demonstrate its for theoretical calculation The experimental result of performance.
In short, photochromic material of the invention shows good photochromic properties under ultraviolet light, and have There is good anti-aging property.The length of conjugated chain has a significant impact their photochromic properties, as molar extinction coefficient, Maximum absorption, cyclisation and open loop body quantum yield.Theoretical calculation further demonstrates their photochromisms in the solution The difference of energy.In addition, the characteristics of being based on aldehyde groups, this Series Molecules can be come as multiduty macromolecular architecture segment Develop novel near-infrared photochromic material.

Claims (6)

1. aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound, it is characterised in that: be formula I and II Shown compound:
Wherein, the integer that n is >=0, R=X (F, Cl, Br, I) and Ar.
2. aldehyde functionsization Dithiophene conjugation extends versatility molecular skeleton compound, it is characterised in that: be shown belowization Close object:
。
3. the preparation that aldehyde functionsization di-thiofuran ethylene conjugation as described in claim 1 extends versatility molecular skeleton compound Method, it is characterised in that:
Using compound shown in formula III as starting material, obtained type I compound (n=0) by witting reaction synthesis, I chemical combination of formula Object (n=0) obtains type I compound (n=1) by witting reaction synthesis, and type I compound (n=1) is closed by witting reaction At obtaining type I compound (n=2), and so on, obtain type I compound (n is >=0 integer)；
Using compound shown in formula IV as starting material, II compound of formula (n=0) is obtained by witting reaction synthesis, formula II is changed It closes object (n=0) and obtains II compound of formula (n=1) by witting reaction synthesis, II compound of formula (n=1) is anti-by witting It should synthesize to obtain II compound of formula (n=2), and so on, obtain II compound of formula (n is >=0 integer)；
。
4. the preparation that aldehyde functionsization di-thiofuran ethylene conjugation as claimed in claim 3 extends versatility molecular skeleton compound Method, it is characterised in that: the preparation method of type I compound (n=0) specifically: (1,3- dioxin -2- is added in anhydrous THF Ethyl-methyl)-triphenylphosphinebromide and NaOMe, the THF solution of III compound of formula is added under nitrogen protection, mixture reflux is anti- It answers, is cooled to room temperature after reaction, through extraction, drying and filtering and concentrating, obtained solid is handled in water with 10% HCl, It stirs at room temperature, 2M NaOH is then added and carries out neutralization reaction, reaction mixture is chromatographed through extraction, drying, filtering and concentrating and column Separation, obtains type I compound (n=0).
5. the preparation that aldehyde functionsization di-thiofuran ethylene conjugation as claimed in claim 3 extends versatility molecular skeleton compound Method, it is characterised in that: the preparation method of II compound of formula (n=0) specifically: (1,3- dioxin -2- is added in anhydrous THF Ethyl-methyl)-triphenylphosphinebromide and NaOMe, the THF solution of IV compound of formula is added under nitrogen protection, mixture reflux is anti- It answers, is cooled to room temperature after reaction, through extraction, drying and filtering and concentrating, obtained solid is dissolved in THF, is existed with 10% HCl It handles in water, stirs at room temperature, 2M NaOH is then added and carries out neutralization reaction, reaction mixture is dense through extraction, drying, filtering Contracting and column chromatography for separation, obtain II compound of formula (n=0).
6. the di-thiofuran ethylene of aldehyde functionsization described in claim 1 conjugation extends versatility molecular skeleton compound in near-infrared Application on photochromic material shows good photochromic properties under ultraviolet light, and has good anti- Ageing properties.
CN201910682255.3A 2019-07-26 2019-07-26 Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application Pending CN110305105A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910682255.3A CN110305105A (en) 2019-07-26 2019-07-26 Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910682255.3A CN110305105A (en) 2019-07-26 2019-07-26 Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application

Publications (1)

Publication Number Publication Date
CN110305105A true CN110305105A (en) 2019-10-08

Family

ID=68081722

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910682255.3A Pending CN110305105A (en) 2019-07-26 2019-07-26 Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application

Country Status (1)

Country Link
CN (1) CN110305105A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111187299A (en) * 2020-01-21 2020-05-22 山西大学 Thieno [3,4-b ] thiophene-based organic photosensitizer and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030118924A1 (en) * 2001-07-30 2003-06-26 Korea Research Institute Of Chemical Technology Diarylethene derivatives and photochromic thin film prepared using the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030118924A1 (en) * 2001-07-30 2003-06-26 Korea Research Institute Of Chemical Technology Diarylethene derivatives and photochromic thin film prepared using the same

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
KAI ALTENHÖNER, ET AL: "Novel Dithienylethenes with Extended π-Systems: Synthesis by Aldol Condensation and Photochromic Properties", 《EUR. J. ORG. CHEM.》 *
NIKOLAY BELIKOV, ET AL: "Photochromic behavior of retinal analogs", 《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY》 *
OLIVER TOSIC, ET AL: "Photochromic dithienylethenes with extended π-systems", 《PHOTOCHEM. PHOTOBIOL. SCI.》 *
YUJIN SEO, ET AL: "A Smart Near-Infrared Fluorescence Probe for Selective Detection of Tau Fibrils in Alzheimer’s Disease", 《ACS CHEM. NEUROSCI.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111187299A (en) * 2020-01-21 2020-05-22 山西大学 Thieno [3,4-b ] thiophene-based organic photosensitizer and preparation method and application thereof
CN111187299B (en) * 2020-01-21 2020-11-06 山西大学 Thieno [3,4-b ] thiophene-based organic photosensitizer and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Feng et al. Photochromic thiophene oligomers based on bisthienylethene: syntheses, photochromic and two-photon properties
AU2008334556B2 (en) Fluorescent, heterocyclic annellated perylene
Avlasevich et al. Novel Core‐Expanded Rylenebis (Dicarboximide) Dyes Bearing Pentacene Units: Facile Synthesis and Photophysical Properties
CN104230953B (en) Benzene-naphthalene diimide and derivant thereof containing 2-(1,3-bis-sulfur/selenium-2-subunit) second cyanogen conjugated structure unit
Hu et al. Dithienylethene-based rotaxanes: synthesis, characterization and properties
Ghorpade et al. Highly sensitive colorimetric and fluorometric anion sensors based on mono and di-calix [4] pyrrole substituted diketopyrrolopyrroles
Guo et al. Visible light-harvesting naphthalenediimide (NDI)-C60 dyads as heavy-atom-free organic triplet photosensitizers for triplet–triplet annihilation based upconversion
Wang et al. Facile synthesis and controllable bromination of asymmetrical intermediates of perylene monoanhydride/monoimide diester
Wu et al. Enhanced luminescence oxygen sensing property of Ru (II) bispyridine complexes by ligand modification
Hu et al. Cyanine-based dithienylethenes: synthesis, characterization, photochromism and biological imaging in living cells
CN107778319A (en) One kind contains seven and condensed cyclic structure indacene A D A type micromolecular compounds and preparation method thereof
CN108864137A (en) A kind of acceptor compound, preparation method, purposes and the photovoltaic cell containing it
Öztürk et al. Perylenebisimide-fullerene dyads as heavy atom free triplet photosensitizers with unique singlet oxygen generation efficiencies
CN110305105A (en) Aldehyde functionsization di-thiofuran ethylene conjugation extends versatility molecular skeleton compound and its preparation method and application
Tatsumi et al. A photo-and halochromic multicolor switching system consisting of diarylethene and malachite green moieties
Li et al. Synthesis, characterization, and nonlinear optical (NLO) properties of truxene-cored diphenylamine derivatives
Hu et al. The photocyclization-dependent ratiometric fluorescent switch: Synthesis, characterization and properties of some terpyridyl-based dithienylethenes
Lee et al. Synthesis and characteristics of dicyanopyrazine dyes containing spiropyran group
Wei et al. Synthesis and thermal polymerization of perylene bisimide containing benzocyclobutene groups
Guo et al. Synthesis and characterization of S, N-heteroacenes by Bischler-Napieralski reaction
Zhang et al. An Optic/Proton Dual‐Controlled Fluorescence Switch based on Novel Photochromic Bithienylethene Derivatives
Zhang et al. The synthesis and properties of linear A–π–D–π–A type organic small molecule containing diketopyrrolopyrrole terminal units
KR100798424B1 (en) Tetrafluorobenzimidazole compounds containing fused aromatic ring
Cai et al. Photochromic dithienylethene-branched triptycene hybrids
CN102850237B (en) Method for preparing asymmetric spirobifluorene compound derived from functional group conversion on different fluorene ring

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20191008