CN109400623A - A kind of novel N-shaped organic semiconducting materials - Google Patents
A kind of novel N-shaped organic semiconducting materials Download PDFInfo
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Abstract
The invention discloses a kind of novel N-shaped organic semiconducting materials, including based on five simultaneously (six and or seven and or ten together) the A-D-A type conjugation small molecule and porphyrin micromolecular of condensed ring unit；Based on five simultaneously (six and or seven and or ten together) the A-D-A type conjugation small molecule of condensed ring unit is design feature according to A-D-A receptor material, change the position of end drawing electron group connection 5-membered aromatic heterocycle, steric hindrance can be reduced, so that material has better steric configuration, it is transmitted conducive to the charge for forming isotropic, and then improves the performance of device；Porphyrin micromolecular is the design feature based on porphyrins, inhale the position β or the meta position of hexa-member heterocycle that electrical end group A is connected to five-ring heterocycles, there is preferable intermolecular charge transfer between porphyrin core and the electrical end group of suction, therefore such compound has preferable charge transport properties, steric hindrance can also be reduced simultaneously, so that material is had better steric configuration, and then improves the performance of device.
Description
Technical field
The present invention relates to a kind of novel N-shaped organic semiconducting materials, including based on five simultaneously (six and or seven and or 11
And) the A-D-A type of condensed ring unit conjugation small molecule and porphyrin micromolecular.It is with five that A-D-A type, which is conjugated small molecule micromolecular,
And (six and or seven and or ten together) condensed ring unit is core, 5-membered aromatic heterocycle is bridging unit, inhales electrical end group A and is connected to
The position β of five-ring heterocycles.Such molecule is applied to organic solar batteries as active layer electron acceptor material, next goes back organic field
Effect transistor, organic detectors etc..Porphyrin micromolecular is using porphyrin unit as core, and five yuan or hexa-atomic aromatic rings are bridging list
Member, the same position β or the meta position of hexa-member heterocycle inhaled electrical end group A and be also connected to five-ring heterocycles.Such molecule can be used as by
Body material is applied to organic solar batteries.
Background technique
With becoming increasingly conspicuous for energy crisis and environmental problem, the mankind must develop and utilize some novel renewable energies
Source.And solar battery is as inexhaustible, nexhaustible clean energy resource, is the best selection for replacing fossil energy.Too
Positive energy battery is efficient Solar use element, in the various solar batteries of scientists preparation, You Jitai
It is positive can battery there is apparent advantage: at low cost, flexible high, environmental-friendly, simple process can print and prepare flexible device etc..
In addition, organic solar batteries are many kinds of, designability is strong, can improve electricity by changing the means such as material and molecular structure
Pond performance, therefore be with a wide range of applications and preferable researching value.In the flow of research of organic solar batteries, grind
The person of studying carefully mainly studies the bulk heteroj junction type organic solar batteries that can simplify manufacture craft, and the type battery is donor material
Material is blended to be formed with acceptor material, so that a reticular structure being intertwined is formed, by reducing exciton transfer distance and expansion
It is big to improve energy conversion efficiency to/acceptor interface area, have many advantages, such as it is at low cost, convenient for manufacturing, quality of materials is light
(Y.Lin, F.Zhao, Y.Wu, K.Chen, Y.Xia, G.Li, S.K.K.Prasad, J.Zhu, L.Huo, H.Bin,
Z.G.Zhang, X.Guo, M.Zhang, Y.Sun, F.Gao, Z.Wei, W.Ma, C.Wang, J.Hodgkiss, Z.Bo, 0.Y.Li, X.Zhan, Mapping Polymer Donors toward High-Efficiency Fullerene
Free Organic Solar Cells, Adv.Mater.2017,29,1604155).
In bulk heterojunction solar cells, the key of preparation high efficiency device is the high performance active material of selection,
I.e. optimal electron donor material and acceptor material.The selection of electron donor material has a diversity, and electron acceptor material
Select it is narrower, depend on fullerene acceptor material in the development of past organic solar batteries, based on fullerene by
The efficiency of the organic solar batteries of body is more than 11%.But the shortcomings that fullerene-based material, also limits organic solar batteries
Development, such as higher energy loss, lower absorption coefficient, not energy level of easy-regulating etc..Then non-fullerene-based material by
It gradually becomes the focus of people's research, compared to fullerene-based material, non-fullerene acceptor material is easy to be chemically modified, and passes through conjunction
The molecule of reason optimizes, and can improve absorption spectrum ranges, molecular entergy level, open-circuit voltage, mobility etc., so as to mention well
The photovoltaic performance of high device obtains the higher organic solar batteries of performance.Therefore, the electron acceptor of design and synthesis narrow band gap
Concern (S.Feng, C.Zhang, Y.Liu, Z.Bi, Z.Zhang, X.Xu, W.Ma, Z.Bo, Fused- of the material by everybody
Ring Acceptors with Asymmetric Side Chains for High-Performance Thick-
FilmOrganic Solar Cells, Adv.Mater.2017,29,1703527).
In recent years, the research in relation to non-fullerene acceptor material be concentrated mainly on benzene-naphthalene diimide, pyrene imidodicarbonic diamide and
It is several systems such as the A-D-A type molecule of representative with ITIC, IEIC, IDT-BR.Wherein, ITIC is that first efficiency breaks through 10%
Electron acceptor material, but since lumo energy is lower, Voc value (0.82-0.94) is not but high, electron mobility values (2.6 ×
10-4cm-1v-1s-1) also below other fullerene-based materials.Li Yongfang seminar carries out side chain isomerism modification, synthesis to ITIC molecule
Small molecule receptor material m-ITIC have biggish absorption coefficient and electron mobility, using J60 as donor material preparation too
It is positive can battery its efficiency can reach 11.77% (Y.Yang, Z.Zhang, H.Bin, S.Chen, L.Gao, L.Xue,
C.Yang, Y.Li, Side-Chain Isomerization on an n-type Organic Semiconductor ITIC
Acceptor Makes 11.77%High Efficiency Polymer Solar Cells, J.Am.Chem.Soc.2016,
138,15011).Hou Jianhui seminar, Institute of Chemistry, Academia Sinica replaces ITIC cyano with condensed ring cyano thiophene indone end group
Indone, design have synthesized non-fullerene acceptor material ITCC, and ITCC is more likely formed orderly packing of molecules, and the LUMO energy of ITCC
Grade is significantly moved up compared to ITIC, is effectively improved open-circuit voltage acquisition and is more than 11% PCE, therefore changes the structure of end group
Be also improve device efficiency performance good method (H.Yao, L.Ye, J.Hou, B.Jang, G.Han, Y.Cui, G.M.Su,
C.Wang, B.Gao, R.Yu, H.Zhang, Y.Yi, H.Y.Woo, H.Ade, J.Hou, Achieving Highly Efficient
Nonfullerene Organic Solar Ceils with Improved Intermolecular Interaction and
Open-Circuit Voltage, Adv.Mater.2017,29,1700254).Compared to ITIC, ITCC, the seminar is former by F
Son introduces receptor unit, and the IT-4F for designing synthesis obtains 13% energy conversion efficiency.IT-4F effectively reduces molecule
Energy level has widened absorption spectrum, improve absorption coefficient and Jsc (W.Zhao, S.Li, H.Yao, S.Zhang, Y.Zhang,
B.Yang, J.Hou, Molecular Optimization Enables over 13%Efficiency in Organic
Solar Cells, J.Am.Chem.Soc., 2017,139,7148).Alkoxy-functional is introduced into non-fowler by the seminar
In the design of alkene electron acceptor, small molecule receptor material IEICO, the HOMO energy level for having synthesized 1.34ev optical band gap is also obvious
It improves.In order to widen the absorption spectrum of IEIC, F atom is introduced receptor unit again simultaneously by them, then designs synthesizing new point
Sub- IEICO-4F, obtain the optical band gap of 1.24ev, while absorption spectrum Einstein shift 200nm or so.It is suitable by selecting
Donor material obtains higher Jsc (35.3mAcm-2), while PCE value is up to 10.9%.(H.Yao, Y.Cui, R.Yu,
B.Gao, H.Zhang, J.Hou, Design, systhesis, and Photovoltaic Characterization of a
Small Molecular with an Ultra-Narrow Band Gap, Angew.Chem, Int.Ed, 2017,56,
3045).Alex K.-Y.Jen seminar is using donor monomer centered on rigid condensed ring thiophene bithiophene (4T), and IC is as end
Base receptor unit, constructs the novel non-fullerene receptor unit 4TIC of highly crystalline rate low band gaps, introduce 4T unit be capable of providing compared with
Low Reorganization Energy realizes lower Voc energy loss.Low band gaps and less energy loss make the lamination sun based on 4TIC
Energy battery obtains 12.62% efficiency (X.Shi, L.Zuo, S.B.Jo, K.Gao, F.Lin, F.Liu, A.K.-Y, JenDesign
of a Highly Crystalline Low-Band Gap Fused-Ring Electron Acceptor for High-
Efficiency Solar Cells with Low Energy Loss, Chem Mater., 2017,29,8369).
A-D-A receptor material has the planar structure of rigidity, has very strong Π-П to interact, with high current-carrying
The condensed ring unit of transport factor is core, and 5-membered aromatic heterocycle is bridging unit, and conjugate planes are outer intermolecular there are four that can reduce
The substituent group of aggregation, both ends introduce can be with the drawing electron group of Effective Regulation energy level, and it is miscellaneous that drawing electron group is connected to 5-membered aromatic
The position α of ring, such as IEICO, ITIC end group are all connected in the position α of thiophene, but so far, all having no any document or patent report
The A-D-A type small molecule receptor material that end group is connected in the position β of five-ring heterocycles is applied to organic solar batteries.
Porphyrin has unique structure, can have preferable light capture ability and photochemical properties by modifying outside ring,
Therefore can be used as active layer material is widely used in organic solar batteries and dye-sensitized solar cells etc.
(S.Chen, L.Yan, L.Xiao, K.Gao, W.Tang, C.Wang, C.Zhu, dX.Wang, F.Liu, X.Peng, W.K.Wong,
X.Zhu, A visible-near-infrared absorbing A-p2-D-p1-D-p2-A type dimeric-
Porphyrin donor for highperformance organic solar cells, J.Mater.Chem.A, 2017,
5,25460).In recent years, porphyrins concentration is designed as p-type donor material, but seldom report N-shaped acceptor material and
And the porphyrin acceptor material performance of report be not very well, PCE value lower than 1% (W.T.Hadmojo, D.Yim, H.Aqoma,
D.Y.Ryu, T.J.Shin, H.W.Kim, E.Hwang, W.D.Jang, I.H.Jung, S.Y.Jang, Artificial light-
Harvesting n-type porphyrin for panchromatic organic photovoltaic devices,
Chem.Sci., 2017,8,5095).Up to now, all have no any document or patent report using porphyrin unit as core, five yuan or
Hexa-atomic aromatic rings is bridging unit, inhales electrical end group A and is connected to the novel of the position β of five-ring heterocycles or the meta position of hexa-member heterocycle
N-shaped acceptor material.
Summary of the invention
The purpose of the present invention is to provide a kind of novel N-shaped organic semiconducting materials, including based on five simultaneously (six and or seven
And or ten together) the A-D-A type conjugation small molecule and porphyrin micromolecular of condensed ring unit；The present invention is prepared for based on five simultaneously (six
And or seven and or ten together) the A-D-A type conjugation small molecule of condensed ring unit changes according to the design feature of A-D-A receptor material
The position for becoming end drawing electron group connection 5-membered aromatic heterocycle, can reduce steric hindrance, so that material has better steric configuration, benefit
It is transmitted in the charge for forming isotropic, and then improves the performance of device.It is small that the present invention is also prepared for a kind of novel porphyrin
Molecule, the design feature based on porphyrins inhale the position β or hexa-member heterocycle that electrical end group A is connected to five-ring heterocycles
Meta position, porphyrin core and inhale and have preferable intermolecular charge transfer between electrical end group, thus such compound have it is preferable
Charge transport properties, while steric hindrance can also be reduced, so that material is had better steric configuration, and then improve the performance of device.
It is of the invention based on five simultaneously (six and or seven and or ten together) the A-D-A type conjugation small molecule of condensed ring unit have with
Lower eight kinds of general structures:
N is 0~2；
Z is C, N or Si；
X is 0, S or Se；
R1, R2 independently are hydrogen, the alkyl of C1~C30, the alkoxy of C1~C30 or 4- alkyl phenyl or 3- alkylbenzene
Base；
Alkyl in the 4- alkyl phenyl or 3- alkyl phenyl is the alkyl of C1~C8；
The R is 2- ethylhexyl or hexyl.
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br in above structure；
R3 is the alkyl of C1~C30 in above structure；
R4 is methyl or methoxy in above structure.
The present invention is to inhale electrical group to be connected in the five of 5-membered aromatic heterocycle β simultaneously (six and or seven simultaneously or ten together) condensed ring list
The A-D-A type of member is conjugated small molecule, preferred embodiment are as follows: the n is 0~1；The z is C, N or Si；The x is 0, S,
Or Se；The R1, R2 independently are hydrogen, the alkyl or 4- hexyl phenyl of C1~C8；Alkyl in the 4- alkyl phenyl
It is the alkyl of C1~C8；The alkyl that R3 in A structure is C1~C8.
The n is 0~1；R1, R2 independently are hydrogen, the alkyl of C1C12, the alkoxy of C1C12 or 4- hexyl phenyl；A
The alkyl that R3 in structure is C1~C8.
The novel porphyrin micromolecular of one kind of the invention has following structure general formula:
M is Fe, Co, Mn, Cu, Zn；
R is 2- ethylhexyl or hexyl.
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br in above structure；
R3 is the alkyl of C1~C30 in above structure；
R4 is methyl or methoxy in above structure.
The present invention is the porphyrin small molecule material inhaled electrical group and be connected in 5-membered aromatic heterocycle β or phenyl ring meta position,
Preferred embodiment are as follows: the M is Fe, Co, Mn, Cu, Zn, and the R is 2- ethylhexyl or hexyl, and R3 is C1 in A structure
The alkyl of~C30, R4 are methyl or methoxy.
It is of the invention based on five simultaneously (six and or seven and or ten together) the preparation side of the A-D-A type conjugated molecule of condensed ring unit
Method includes following two step:
Step 1: by with R1, R2 substituent group five simultaneously (six and or seven and or ten together) condensed ring unit tin trimethyl
Object and three band aldehyde radicals are closed, five five member ring heterocyclic compounds (thiophene or thiazole) with bromine are added in reaction vessel, wherein containing
The molar ratio of tin compound and five member ring heterocyclic compound is 1: 2~5；Using toluene as solvent, it is passed through inert gas discharge reactor
In air after, the tetrakis triphenylphosphine palladium catalyst of catalytic amount is added, temperature be 100~200 DEG C under the conditions of be stirred,
After reaction, it purifies to obtain the molecule for having following structure general formula by chromatographic column:
N is 0~2；
Z is C, N or Si；
X is 0, S or Se；
R1, R2 independently are hydrogen, the alkyl of C1~C30, the alkoxy of C1~C30 or 4- alkyl phenyl or 3- alkylbenzene
Base；
Alkyl in the 4- alkyl phenyl or 3- alkyl phenyl is the alkyl of C1~C8；
The additional amount of the tetrakis triphenylphosphine palladium catalyst and the molar ratio of the tin trimethyl compound are 1:
10~100；
The temperature is 100~200 DEG C, and the time for reacting progress is 12~48 hours.
Step 2: above-mentioned be added to the aldehyde compound of five-ring heterocycles with drawing electron group A containing condensed ring unit is reacted
In container, the molar ratio of aldehyde compound and drawing electron group A are 1:2~100；Using chloroform as solvent, lead to inert gas discharge
Then pyridine or piperidines is added in air in reaction vessel, be 30~80 DEG C small be stirred to react in temperature；Reaction terminates
Afterwards, gained reaction product is poured into methanol solution, filtration drying obtains solid, is purified with column chromatography, obtains following five simultaneously
(six and seven and or ten together) the A-D-A type of condensed ring unit is conjugated small molecule:
N is 0~1；
Z is C, N or Si；
X is O, S or Se；
R1, R2 independently are hydrogen, the alkyl of C1~C30, the alkoxy of C1~C30 or 4- alkyl phenyl or 3- alkylbenzene
Base；
Alkyl in the 4- alkyl phenyl or 3- alkyl phenyl is the alkyl of C1~C8.
Drawing electron group A structure is selected from one of following structures:
Described M=F, Cl or the Br；
The R3 is the alkyl of C1~C30；
The R4 is methyl or methoxy；
The additional amount of the pyridine or piperidines and the molar ratio of the aldehyde compound are 1: 0.005~0.5；
The temperature is 30~80 DEG C, and the reaction time of progress is 6~48 hours；
It is of the invention based on five simultaneously (six and seven and or ten together) the A-D-A type conjugation small molecule of condensed ring unit possesses
Stronger absorption coefficient, higher transmission performance and suitable energy level can be used as acceptor material applied to organic solar electricity
Pond.
The preparation method following steps of porphyrin micromolecular:
Aldehyde compound with five-ring heterocycles or phenyl ring and drawing electron group A is dissolved in propionic acid solution and is added to
After reaction vessel, the propionic acid solution dissolved with existing steaming pyrroles is added after being heated to reflux, wherein aldehyde compound and pyrroles's rubs
You are than being 1: 1.Reaction reflux one hour after nitrobenzene is added, keep this it is temperature-resistant continue stirring one hour.After reaction
It is cooled to room temperature precipitation porphyrin compound, filtering precipitating is purified to by column chromatography and has following structure that the porphyrin of general formula is new
Type small molecule compound:
M is Fe, Co, Mn, Cu, Zn；
R is 2- ethylhexyl or hexyl.
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br；
R3 is the alkyl of C1~C30；
R4 is methyl or methoxy；
The aldehyde compound is 1: 1 with the molar ratio for now steaming pyrroles；
The time reacted under the reflux temperature is 2 hours.
The present invention is based on porphyrin new small molecule compound can be used as active layer electron acceptor material be applied to it is organic too
Positive energy battery
Specific embodiment
Embodiment one:
The synthetic route of aldehyde compound containing condensed ring unit and five-ring heterocycles is as follows:
Compound A (0.12mmol) is added in reaction flask, compound B (0.3mmol) and 10mL now steam toluene, vacuumize
Back and forth three times, Pd (PPh is added in logical nitrogen3)4(7.6mg), temperature are 110 DEG C, are stirred 48 hours；It is cooled to room temperature, it is anti-in gained
It answers and deionized water is added in object, CHCl2It is extracted, gained organic phase is dry with anhydrous magnesium sulfate；It filters and is spin-dried for removing molten
After agent, use petroleum ether/methylene chloride mixed solvent (volume ratio 2: 1) as eluent, silica gel (200~300 mesh) column chromatography
Separating-purifying is carried out, yellow solid, the as molecule 1 containing hexa-atomic condensed ring and aldehyde radical are obtained.
Embodiment two:
The synthetic route of A-D-A type conjugated molecule containing condensed ring unit is as follows:
Compound 1 (0.03mmol) and compound C (0.18mmol) are added in reaction flask and now steams chloroform 10mL, leads to
To remove the air in reaction flask, piperidines is then added within nitrogen 30 minutes, temperature is 65 DEG C and stirs 12 hours；It is cooled to room temperature,
Reaction solution is poured into methanol, uses petroleum ether/methylene chloride mixed solvent as eluent, silica gel after the precipitating being obtained by filtration
(200~300 mesh) column chromatography carries out separating-purifying, as the A-D-A type conjugated molecule 2 containing condensed ring unit.
Embodiment three:
Compound A (0.12mmol) is added in reaction flask and compound D (0.3mmol) and 10mL now steams toluene, takes out
Vacuum leads to nitrogen and Pd (PPh is added afterwards three times back and forth3)4(7.6mg), temperature are 110 DEG C, are stirred 48 hours；It is cooled to room temperature,
Deionized water, CHCl are added in gained reactant2It is extracted, gained organic phase is dry with anhydrous magnesium sulfate；It filters and is spin-dried for
After removing solvent, use petroleum ether/methylene chloride mixed solvent as eluent, silica gel (200~300 mesh) column chromatography is separated
Purification obtains solid product, as contains the molecule 3 of five yuan of condensed ring and aldehyde radical.
Example IV:
Compound 3 (0.03mmol) and compound E (0.18mmol) are added in reaction flask and now steams chloroform 10mL, leads to
To remove the air in reaction flask, piperidines is then added within nitrogen 30 minutes, temperature is 65 DEG C and stirs 12 hours；It is cooled to room temperature,
Reaction solution is poured into methanol, uses petroleum ether/methylene chloride mixed solvent as eluent, silica gel after the precipitating being obtained by filtration
(200~300 mesh) column chromatography carries out separating-purifying, as the A-D-A type conjugated molecule 4 containing condensed ring unit.
Embodiment five:
60mL propionic acid and compound G (8mmol) are added in reaction flask, 5mL is added dropwise after being heated to reflux dissolved with pyrroles
40mL nitrobenzene is added after reaction reflux one hour in the propionic acid solution of (8mmol), continues reflux 1 hour, cold after reaction
But to room temperature, porphyrin compound is precipitated, filters out solid, is purified by column chromatography.
Claims (6)
1. one kind is conjugated small molecule based on the A-D-A type of five simultaneously (six and or seven simultaneously) condensed ring unit, it is characterized in that: it is described based on
Five simultaneously the A-D-A type conjugation small molecule of (six and or seven simultaneously) condensed ring unit has following eight kinds of general structures:
N is 0~2；
Z is C, N or Si；
X is 0, S or Se；
R1, R2 independently are hydrogen, the alkyl of C1~C30, the alkoxy of C1~C30 or 4- alkyl phenyl or 3- alkyl phenyl；
Alkyl in 4- alkyl phenyl or 3- alkyl phenyl is the alkyl of C1~C8；
R is 2- ethylhexyl or hexyl.
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br in above structure；
R3 is the alkyl of C1~C30 in above structure；
R4 is methyl or methoxy in above structure.
2. a kind of novel porphyrin micromolecular, it is characterized in that: the novel porphyrin micromolecular of described one kind has following structure
General formula:
M is Fe, Co, Mn, Cu, Zn；
R is 2- ethylhexyl or hexyl；
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br in above structure；
R3 is the alkyl of C1~C30 in above structure；
R4 is methyl or methoxy in above structure.
3. the A-D-A conjugation small molecule according to claim 1 for being based on five simultaneously (six and seven simultaneously) condensed ring unit, special
Sign is: the n is 0~1；The z is C, N or Si；The x is 0, S or Se；The R1, R2 independently are hydrogen,
The alkyl or 4- hexyl phenyl of C1~C8；Alkyl in the 4- alkyl phenyl is the alkyl of C1~C8；R3 in A structure is
The alkyl of C1~C8.
4. the A-D-A conjugation small molecule according to claim 1 for being based on five simultaneously (six and seven simultaneously) condensed ring unit, special
Sign is: the n is 0~1；R1, R2 independently are hydrogen, the alkyl of C1 C12, the alkoxy of C1 C12 or 4- hexyl phenyl；A
The alkyl that R3 in structure is C1~C8.
5. the A-D-A conjugation small molecule according to claim 1 for being based on five simultaneously (six and seven simultaneously) condensed ring unit, special
Sign is: the preparation method based on the five simultaneously A-D-A conjugation small molecule of (six and seven simultaneously) condensed ring unit the following steps are included:
Step 1: by five simultaneously (six and or seven simultaneously) condensed ring unit tin trimethyl compound and three bands with R1, R2 substituent group
Aldehyde radical, five five member ring heterocyclic compounds (thiophene or thiazole) with bromine are added in reaction vessel, wherein sn-containing compound and five
The molar ratio of membered heterocyclic compound is 1: 2~5；Using toluene as solvent, after being passed through the air in inert gas discharge reactor, add
The tetrakis triphenylphosphine palladium catalyst for entering catalytic amount is stirred under the conditions of temperature is 100~200 DEG C: after reaction, being led to
Chromatographic column is crossed to purify to obtain the molecule for having following structure general formula:
N is 0~2；
Z is C, N or Si；
X is 0, S or Se；
R1, R2 independently are hydrogen, the alkyl of C1~C30, the alkoxy of C1~C30 or 4- alkyl phenyl or 3- alkyl phenyl；4-
Alkyl in alkyl phenyl or 3- alkyl phenyl is the alkyl of C1~C8；
R is 2- ethylhexyl or hexyl；
The molar ratio of the additional amount of the tetrakis triphenylphosphine palladium catalyst and the tin trimethyl compound is 1: 10~
100；It is stirred under the conditions of temperature is 100~200 DEG C, the time for reacting progress is 12~48 hours.
Step 2: the above-mentioned aldehyde compound containing condensed ring unit and five-ring heterocycles and drawing electron group A are added to reaction vessel
In, the molar ratio of aldehyde compound and drawing electron group A are 1: 2~100；Using chloroform as solvent, lead to inert gas discharge reaction
Then pyridine or piperidines is added in air in container, be 30~80 DEG C small be stirred to react in temperature；After reaction, will
Gained reaction product is poured into methanol solution, and filtration drying obtains solid, is purified with column chromatography, and obtaining following five, simultaneously (six simultaneously
Or seven simultaneously) the A-D-A type of condensed ring unit is conjugated small molecule:
N is 0~1；
Z is C, N or Si；
X is 0, S or Se；
R1, R2 independently are hydrogen, the alkyl of C1~C30, the alkoxy of C1~C30 or 4- alkyl phenyl or 3- alkyl phenyl；
Alkyl in the 4- alkyl phenyl or 3- alkyl phenyl is the alkyl of C1~C8.
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br；
R3 is the alkyl of C1~C30；
R4 is methyl or methoxy；
The additional amount of the pyridine or piperidines and the molar ratio of the aldehyde compound are 1: 0.005~0.5；It is in temperature
It is 30~80 DEG C small to be stirred to react；The reaction time of progress is 6~48 hours.
6. the novel porphyrin micromolecular of one kind according to claim 2, it is characterized in that: the preparation side of porphyrin micromolecular
Method the following steps are included:
Aldehyde compound with five-ring heterocycles or phenyl ring and drawing electron group A is dissolved in propionic acid solution and is added to reaction
After container, the propionic acid solution dissolved with existing steaming pyrroles is added after being heated to reflux, wherein the molar ratio of aldehyde compound and pyrroles
For 1:1.Reaction reflux one hour after nitrobenzene is added, keep this it is temperature-resistant continue stirring one hour.It cools down after reaction
Porphyrin compound is precipitated to room temperature, filtering precipitating is purified to by column chromatography and has following structure that the porphyrin of general formula is novel small
Molecular compound:
M is Fe, Co, Mn, Cu, Zn；
R is 2- ethylhexyl or hexyl；
Drawing electron group A structure is selected from one of following structures:
G=F, Cl or Br；
R3 is the alkyl of C1~C30；
R4 is methyl or methoxy.
The aldehyde compound is 1: 1 with the molar ratio for now steaming pyrroles；The time reacted under the reflux temperature is 2 small
When.
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