CN106946737A - Pyrene fluorobenzene hydrazone and its preparation method and application - Google Patents
Pyrene fluorobenzene hydrazone and its preparation method and application Download PDFInfo
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- CN106946737A CN106946737A CN201710187486.8A CN201710187486A CN106946737A CN 106946737 A CN106946737 A CN 106946737A CN 201710187486 A CN201710187486 A CN 201710187486A CN 106946737 A CN106946737 A CN 106946737A
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- fluorobenzene
- acetic acid
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- -1 Pyrene fluorobenzene hydrazone Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003287 optical effect Effects 0.000 claims abstract description 20
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Chemical group 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000004031 phenylhydrazines Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000001632 sodium acetate Substances 0.000 claims abstract description 8
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 5
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 claims abstract description 3
- 229940125904 compound 1 Drugs 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229940125782 compound 2 Drugs 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 2
- KOERXYXZTJFKMN-UHFFFAOYSA-N fluorobenzene pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.FC3=CC=CC=C3 KOERXYXZTJFKMN-UHFFFAOYSA-N 0.000 abstract description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- OHUWRYQKKWKGKG-UHFFFAOYSA-N formaldehyde;pyrene Chemical group O=C.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 OHUWRYQKKWKGKG-UHFFFAOYSA-N 0.000 abstract 1
- 229960004249 sodium acetate Drugs 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 229940126214 compound 3 Drugs 0.000 description 10
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FEKUXLUOKFSMRO-UHFFFAOYSA-N (4-fluorophenyl)hydrazine;hydron;chloride Chemical class Cl.NNC1=CC=C(F)C=C1 FEKUXLUOKFSMRO-UHFFFAOYSA-N 0.000 description 2
- WKUKMWULNCPAON-UHFFFAOYSA-N Cl.NN.FC1=CC=CC(=C1)F Chemical compound Cl.NN.FC1=CC=CC(=C1)F WKUKMWULNCPAON-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent 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
- C09K2211/1007—Non-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
- C09K2211/1003—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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to third order non-linear optical material field, a kind of pyrene fluorobenzene hydrazone and its preparation method and application is disclosed.Its formula is as follows：, wherein, R1~R5In at least one be F, it is other then be H.By 1 pyrene formaldehyde, fluorine substituted phenylhydrazines or its hydrochloride salt in methyl alcohol, glacial acetic acid or glacial acetic acid and sodium acetate are added, is stirred, 4 ~ 5h is heated to reflux, cold filtration, purifying produces target product.Pyrene fluorobenzene hydrazone synthetic route of the present invention is simple, with low cost, processing is convenient and yield is higher, there is larger development prospect.Pyrene fluorobenzene of the present invention shows good third-order non-linear absorbent properties in the femtosecond laser Z sweep tests at 515 nm, illustrate that the invention pyrene fluorobenzene can turn into potential third order non-linear optical material, and the present invention may be selected different electron withdraw groups to adjust third order non-linear optical property.
Description
Technical field
The invention belongs to third order non-linear optical material field, and in particular to pyrene-fluorobenzene hydrazone and its preparation method and application.
Background technology
It is various due to what is nonlinear polarization occur and produce after third-order nonlinear optical effect refers to that material is acted on high light
Optical physics phenomenon.Third order non-linear optical material is limited and threshold value in optical communication, the control of optical information processing remaining light signal, light
Tempting application prospect is shown in terms of monitoring, optical computer, therefore explores the research of new third order non-linear optical material
With development, the attention of scientists from all over the world is constantly subjected to.Organic molecule third order non-linear optical material is because with wide sound
Answer wave band, good pliability, high light injury threshold and lower cost, be readily synthesized, can be reduced and modify etc. excellent
Put and receive much concern.
The content of the invention
It is an object of the invention to provide a kind of pyrene-fluorobenzene hydrazone and its preparation method and application.
To achieve the above object, the technical scheme that the present invention takes is as follows：
Pyrene-fluorobenzene hydrazone, its formula is as follows：
, wherein, R1~R5In at least one be F, it is other then be H.
Preferably, the pyrene-fluorobenzene hydrazone is compound 1, compound 2, compound 3 or compound 4, the knot of compound 1 ~ 4
Structure formula is respectively：
、、、。
The invention provides two methods, it is specially：
Preparation method is 1.：By 1- pyrene formaldehydes, the dissolving of fluorine substituted phenylhydrazines in methyl alcohol, glacial acetic acid is added, stirs, is heated to reflux
（68~75℃）4 ~ 5h, cold filtration, purifying produces target product.
Preferably, by a mole volume basis, 1- pyrene formaldehydes: fluorine substituted phenylhydrazines: methanol: glacial acetic acid=1mmoL: 1 ~ 1.5
mmoL∶18~23mL∶0.4~0.6mL。
Preparation method is 2.：By 1- pyrene formaldehydes, fluorine substituted phenylhydrazines hydrochloride salt in methyl alcohol, sodium acetate and ice vinegar are added
Acid, stirring, is heated to reflux（68~75℃）4 ~ 5h, cold filtration, purifying produces target product.
Preferably, by a mole volume basis, 1- pyrene formaldehydes: fluorine substituted phenylhydrazines hydrochloride: methanol: sodium acetate: glacial acetic acid=
1mmoL∶1~1.5 mmoL∶18~23mL∶1~1.5 mmoL∶0.4~0.6mL。
The raw material that differs only in of two kinds of preparation methods is fluorine substituted phenylhydrazines or its hydrochloride, when selection fluorine substituted phenylhydrazines
During as raw material, it is not necessary to add sodium acetate, and when selecting fluorine substituted phenylhydrazines hydrochloride as raw material, then need to add acetic acid
Sodium.
The pyrene-fluorobenzene hydrazone as third order non-linear optical material application.
Numerous studies show to be formed effective push-and-pull electronics to being the key for producing third order non-linear optical property, meanwhile,
Molecule with resonant structure also tends to show well due to the electron delocalization with bidirectional electronic transfer ability and height
Third order non-linear optical property.Therefore, on the basis of theoretical herein the present invention synthesized using-NH-N=CH- structures as parent,
Pyrene with push-and-pull electronics pair-fluorobenzene hydrazone compound, wherein, the fluorobenzene of difference substitution is that electron withdraw group, pyrenyl are electron
Group, forms effective electron donor-acceptor structure.
Beneficial effect：
Pyrene of the present invention-fluorobenzene hydrazone synthetic route is simple, with low cost, processing is convenient and yield is higher, there is larger hair
Exhibition prospect.Pyrene-fluorobenzene of the present invention shows good third-order non-linear and absorbed in the femtosecond laser Z sweep tests at 515 nm
Property, illustrates that the invention pyrene-fluorobenzene can turn into potential third order non-linear optical material, and different electrophilics may be selected in the present invention
Group adjusts third order non-linear optical property.Meanwhile, the results show electron-withdrawing group electron-withdrawing power more strong nonlinearity is more
Good, the present invention also provides thinking to probe into third order non-linear optical material.
Brief description of the drawings
Fig. 1：Compound 1 ~ 4 (5 × 10-5M) the ultraviolet-visible absorption spectroscopy in DMF, 1- compounds 1,2- compounds 2,
3- compounds 3,4- compounds 4.
Fig. 2：Compound 1（1mg/mL）Perforate Z scanning curves under 515 nm wavelength femtosecond lasers.
Fig. 3：Compound 2（1mg/mL）Perforate Z scanning curves under 515 nm wavelength femtosecond lasers.
Fig. 4：Compound 3（1mg/mL）Perforate Z scanning curves under 515 nm wavelength femtosecond lasers.
Fig. 5：Compound 4（1mg/mL）Perforate Z scanning curves under 515 nm wavelength femtosecond lasers.
Fig. 6：Perforate Z scanning curve of the solvent DMF under 515 nm wavelength femtosecond lasers.
Embodiment
Embodiment 1
The structural formula of compound 1 is：
；
The synthetic route of compound 1 is as follows：
；
The synthesis step of compound 1：By the methanol solution of 1- pyrene formaldehydes（The mL methanol of 0.5 mmol 1- pyrene formaldehydes+15）It is added drop-wise to
The methanol solution of 4- fluorophenyl hydrazine hydrochlorides and sodium acetate（The mL first of 0.7mmol 4- fluorophenyl hydrazine hydrochloride+0.7mmol sodium acetates+5
Alcohol）In, then add 0.5 mL glacial acetic acid, 70 DEG C of heating stirrings 5 h of backflow, cold filtration, with dichloromethane and recrystallizing methanol
（V(DCM)∶V(MeOH)=1∶3）, you can obtain final product compound 1.
Compound 1 is characterized as below：HRMS (EI) m/z: calcd for C23H15FN2Na [M + Na]+,
361.1200; found, 361.0000. 1H NMR (400 MHz, DMSO-d6, TMS): δH10.70 (s, 1H),
8.90 (s, 1H), 8.75 (d, 1H), 8.57(t, 1H), 8.31 (dd, 4H), 8.19 (s, 2H), 8.09
(t,1H), 7.21(dd, 2H) and 7.15 (t, 2H)。
Embodiment 2
The structural formula of compound 2 is：
；
The synthetic route of compound 2 is as follows：
；
The synthesis step of compound 2：By the methanol solution of 1- pyrene formaldehydes（The mL methanol of 0.5 mmol 1- pyrene formaldehydes+15）It is added drop-wise to
The methanol solution of 2,4 difluorobenzene hydrazine hydrochloride and sodium acetate（0.7mmol 2,4 difluorobenzene hydrazine hydrochloride+0.7mmol sodium acetates
+ 5 mL methanol）In, then adding 0.5 mL glacial acetic acid, 70 DEG C of heating stirrings 5 h of backflow, cold filtration uses column chromatography（V(PE)∶
V(DCM)=10∶1）Purification, you can obtain final product compound 2.
Compound 2 is characterized as below：HRMS (EI) m/z: calcd for C23H14F2N2Na[M + Na]+,
379.3800; found, 379.0000. 1HNMR (400 MHz, DMSO-d6, TMS): δH10.51 (s, 1H),
9.24 (s, 1H), 8.67 (d, 1H), 8.61 (d, 1H), 8.32 (d, 4H), 8.20 (s, 2H), 8.10 (t,
1H), 7.67 (td, 1H), 7.29 (dd, 1H) and 7.09 (t, 1H).
Embodiment 3
The structural formula of compound 3 is：
；
The synthetic route of compound 3 is as follows：
；
The synthesis step of compound 3：By the methanol solution of 1- pyrene formaldehydes（The mL methanol of 0.5 mmol 1- pyrene formaldehydes+15）It is added drop-wise to
The methanol solution of 2,3,5,6- tetrafluoro phenylhydrazines（The mL methanol of 0.7 mmol 2,3,5,6- tetrafluoros phenylhydrazine+5）In, then add 0.5 mL ice
Acetic acid, 70 DEG C of heating stirrings 5 h of backflow, cold filtration uses column chromatography（V(PE)∶V(DCM)=8∶1）Purification, you can obtain final
Product Compound 3.
Compound 3 is characterized as below：HRMS (EI) m/z: calcd for C23H12F4N2Na[M + Na]+,
415.0900; found, 414.9000. 1HNMR (400 MHz, DMSO-d6, TMS): δH10.71 (s, 1H),
9.23 (s, 1H), 8.79 (d, 1H), 8.44 (t, 1H), 8.33 (dd, 4H), 8.21 (q, 2H), 8.11 (t,
1H), 7.33 – 7.18 (m, 1H)。
Embodiment 4
The structural formula of compound 4 is：
；
The synthetic route of compound 4 is as follows：
；
The synthesis step of compound 4：By the methanol solution of 1- pyrene formaldehydes（The mL methanol of 0.5 mmol 1- pyrene formaldehydes+15）It is added drop-wise to
The methanol solution of phenyl-pentafluoride hydrazine（The mL methanol of 0.7 mmol phenyl-pentafluorides hydrazine+5）In, then adding 0.5 mL glacial acetic acid, 70 DEG C of heating are stirred
5 h of backflow are mixed, cold filtration uses column chromatography（V(PE)∶V(DCM)=8∶1）Purification, you can obtain final product compound 4.
Compound 4 is characterized as below：HRMS (EI) m/z: calcd for C23H11F5N2Na[M + Na]+,
433.0800; found, 432.9000. 1HNMR (400 MHz, DMSO-d6, TMS): δH10.54 (s, 1H),
9.18 (s, 1H), 8.76 (d, 1H), 8.44 (d, 1H), 8.35-8.30 (m, 4H), 8.21 (q, 2H),
8.11 (t, 1H)。
It is 5 × 10 that compound 1 ~ 4 is made into concentration respectively-5Mol/L DMF solution, determines its UV absorption.Compound
1 ~ 4 (5 × 10 in DMF-5M ultraviolet-visible absorption spectroscopy) is shown in Fig. 1.As seen from the figure：From compound 1 to compound 4, with suction
The enhancing of electronics base electron-withdrawing power, the maximal ultraviolet absorption peak of compound 1 ~ 4 blue shift successively, their absorption peak position according to
Secondary is 412nm, 400nm, 386nm, 384nm.
Third-order non-linear absorption characteristic research is carried out using femtosecond laser Z scan methods respectively to compound 1 ~ 4：Laser
The wavelength of output is 515 nm, and pulsewidth is 260 fs, extracts DMF solution of the 0.5 mL concentration for 1mg/mL compound, injection
To thickness in 2 mm quartz colorimetric utensil, then cuvette to be placed on loading translation stage and measured, focal length of convex lens
For 300 mm, the laser energy of focal point is 40 nj, under these conditions, does perforate Z scannings to the DMF solution of compound and grinds
Study carefully, and data are fitted.In addition, replacing the DMF solution of above-claimed cpd with the DMF of equivalent, perforate Z is to solvent DMF
Scanning research, and data are fitted.
The perforate Z scanning curves of compound 1 are as shown in Figure 2.Compound 1 shows as anti-saturated absorption, and transmitance is 87%, β
It is worth and is：4×10-14 W/m。
The perforate Z scanning curves of compound 2 are as shown in Figure 3.Compound 2 shows as saturated absorption, and transmitance is 78%, β value
For：-1.1×10-13 W/m。
The perforate Z scanning curves of compound 3 are as shown in Figure 4.Compound 3 shows as anti-saturated absorption, and transmitance is 92%, β
It is worth and is：1.8×10-13 W/m。
The perforate Z scanning curves of compound 4 are as shown in Figure 5.Compound 4 shows as anti-saturated absorption, and transmitance is 93%, β
It is worth and is：1.3×10-13 W/m。
The perforate Z scanning curves of solvent DMF are as shown in Figure 6.The transmitance of DMF solution is 93%, and β value is：0.
Experimental result is shown：
Due to compound 1 ~ 4 near 515 nm in without UV absorption phenomenon（See Fig. 1）, thereby determine that 515 nm optical maser wavelengths
Under generation third-order non-linear be not due to caused by imparted absorption the reason for absorb, nor caused by solvent DMF（See figure
6）, but caused by compound 1 ~ 4 itself.
Compound 1,3,4 shows as non-linear anti-saturated absorption, and compound 2 then shows as non-linear saturated absorption, says
The position of bright fluoro substituents has a great impact to non-line absorption, and absorption of the absorption coefficient than compound 1 of compound 3 and 4
Coefficient is higher by an order of magnitude, illustrates that third-order non-linear, which absorbs, also to be strengthened with the increase of fluorine atom number on electron-withdrawing group.
Above-described embodiment is used for illustrating this patent, rather than this patent is limited, this patent spirit with
In scope of the claims, any modifications and changes made to this patent both fall within the protection domain of this patent.
Claims (7)
1. pyrene-fluorobenzene hydrazone, it is characterised in that its formula is as follows：
, wherein, R1~R5In at least one be F, it is other then be H.
2. pyrene as claimed in claim 1-fluorobenzene hydrazone, it is characterised in that：The pyrene-fluorobenzene hydrazone is compound 1, compound 2, chemical combination
Thing 3 or compound 4, the structural formula of compound 1 ~ 4 is respectively：
、、、。
3. prepare the method for pyrene as claimed in claim 1 or 2-fluorobenzene hydrazone, it is characterised in that：By 1- pyrene formaldehydes, fluorine substituted phenylhydrazines
Dissolving in methyl alcohol, adds glacial acetic acid, stirs, and is heated to reflux 4 ~ 5h, and cold filtration, purifying produces target product.
4. method as claimed in claim 3, it is characterised in that：By a mole volume basis, 1- pyrene formaldehydes: fluorine substituted phenylhydrazines: methanol:
MmoL: 18 ~ 23mL: the 0.4 ~ 0.6mL of glacial acetic acid=1mmoL: 1 ~ 1.5.
5. prepare the method for pyrene as claimed in claim 1 or 2-fluorobenzene hydrazone, it is characterised in that：By 1- pyrene formaldehydes, fluorine substituted phenylhydrazines
Hydrochloride salt in methyl alcohol, adds sodium acetate and glacial acetic acid, stirring, is heated to reflux 4 ~ 5h, and cold filtration, purifying is produced
Target product.
6. method as claimed in claim 5, it is characterised in that：By a mole volume basis, 1- pyrene formaldehydes: fluorine substituted phenylhydrazines hydrochloride
: methanol: sodium acetate: mmoL: 18 ~ 23mL: 1 ~ 1.5mmoL: the 0.4 ~ 0.6mL of glacial acetic acid=1mmoL: 1 ~ 1.5.
7. pyrene as claimed in claim 1 or 2-fluorobenzene hydrazone is used as the application of third order non-linear optical material.
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| CN101852996A (en) * | 2009-03-31 | 2010-10-06 | 京瓷美达株式会社 | Single layer type electrophotographic photoconductor and image forming device |
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| CN101852996A (en) * | 2009-03-31 | 2010-10-06 | 京瓷美达株式会社 | Single layer type electrophotographic photoconductor and image forming device |
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| CN111082295A (en) * | 2019-12-31 | 2020-04-28 | 陕西师范大学 | Mode-locked pulse light source based on hydrazone organic matter and preparation method |
| CN111082295B (en) * | 2019-12-31 | 2021-08-06 | 陕西师范大学 | Mode-locked pulse light source based on hydrazone organic matter and preparation method |
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