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CN-122010926-A - Bidicarbazole benzothiadiazole compound, preparation method and co-sensitization application thereof

CN122010926ACN 122010926 ACN122010926 ACN 122010926ACN-122010926-A

Abstract

The invention discloses a biscarbazole benzothiadiazole compound, a preparation method and a co-sensitization application thereof, which are characterized in that the compound shown in a formula (II) and cyanoacetic acid or rhodamine-3-acetic acid are dissolved in a solvent, adding an alkali catalyst, stirring, heating and refluxing for reaction, concentrating after the reaction is finished, separating and purifying the obtained concentrate by column chromatography silica gel after the concentrate is dissolved in the eluent, collecting the eluent, evaporating the eluent to obtain the target compound, and using the target compound for preparing the dye sensitizer. According to the invention, two N-butylcarbazole electron donors are connected by using benzothiadiazole, then an anchoring group and an electron acceptor cyanoacetic acid or rhodamine-3-acetic acid are introduced into the benzothiadiazole, or a cyanoacetic acid acceptor is connected by a styrene bridge, so that the biscarbazole benzothiadiazole compound is synthesized, and a new applicable substance is added for the screening of dye sensitizers.

Inventors

  • HAN LIANG
  • Fei Angcheng
  • ZHOU RUI
  • YE QING
  • LI YUJIN

Assignees

  • 浙江工业大学

Dates

Publication Date
20260512
Application Date
20260106

Claims (10)

  1. 1. The biscarbazole benzothiadiazole compound is characterized in that the molecular structure is shown as a formula (ZR-2), a formula (ZR-5), a formula (ZR-6), a formula (ZR-7), a formula (ZR-8) or a formula (ZR-9); 。
  2. 2. A process for preparing a biscarbazole benzothiadiazole compound according to claim 1, characterized in that a compound represented by the formula (IIa), the formula (IIb), the formula (IIc), the formula (IId) and the formula (IIe) and cyanoacetic acid or rhodamine-3-acetic acid are dissolved in a solvent, a base catalyst is added, stirring, heating and reflux reaction is carried out, the solvent is removed after the reaction is finished, the obtained concentrate is dissolved in an eluent, separation and purification are carried out through column chromatography silica gel, and eluent is collected and distilled to remove the eluent, thus obtaining the target product; the structural formulas of the compounds shown in the formulas (IIa), (IIb), (IIc), (IId) and (IIe) are as follows: 。
  3. 3. The preparation method of the biscarbazole benzothiadiazole compound, according to claim 2, is characterized in that the mass ratio of the compound shown in the formula (IIa), the formula (IIb), the formula (IIc), the formula (IId) or the formula (IIe) to the base catalyst is 1:6-10.
  4. 4. The process for preparing biscarbazole benzothiadiazole compound according to claim 2, characterized in that the base catalyst used is piperidine.
  5. 5. The method for preparing the biscarbazole benzothiadiazole compound according to claim 2, characterized in that the heating reflux reaction time is 10 h.
  6. 6. The method for preparing the biscarbazole benzothiadiazole compound according to claim 2, wherein the molar ratio of the compound represented by the formula (IIa), the formula (IIb), the formula (IIc), the formula (IId) or the formula (IIe) and the cyanoacetic acid or the rhodamine-3-acetic acid is 1:5-12.
  7. 7. The preparation method of the biscarbazole benzothiadiazole compound according to claim 2, wherein the solvent is a mixed solvent of acetonitrile and chloroform, and the volume ratio of acetonitrile to chloroform is 2:1.
  8. 8. The method for producing a biscarbazole benzothiadiazole compound according to claim 2, wherein the ratio of the amount of a substance of the compound represented by formula (IIa), formula (IIb), formula (IIc), formula (IId) or formula (IIe) to the volume of the solvent is 1:40 to 75, the amount of the substance is in mmol, and the volume is in mL.
  9. 9. The preparation method of the biscarbazole benzothiadiazole compound according to claim 2, wherein the eluent is a mixed solvent consisting of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 20:1.
  10. 10. Use of a biscarbazole benzothiadiazole compound according to claim 1 in a dye sensitizer.

Description

Bidicarbazole benzothiadiazole compound, preparation method and co-sensitization application thereof Technical Field The invention relates to a biscarbazole benzothiadiazole compound, a preparation method and application thereof. Background Compared with metal organic dye sensitizers, nonmetal organic dye sensitizers are widely studied and paid attention to because of the advantages of easily available raw materials, high molar absorptivity, remarkable performance improvement only by fine structure regulation and control, and the like. Among the many electron-rich units, carbazole has become an important class of electron donor materials due to its large conjugated planar structure, good flexibility in molecular design, and excellent hole transport capability. In recent years, research on carbazole-based dye sensitizers has been continuously emerging, exhibiting excellent photoelectric conversion efficiency. On the other hand, electron-withdrawing benzothiadiazole units are also frequently present in dye sensitizer structures, which often act as co-acceptors, increasing the molecular conjugation system, promoting intramolecular charge transfer, and further optimizing the energy level while widening the molecular absorption spectrum. Therefore, the invention combines the dicarbazole donor unit and the benzothiadiazole acceptor unit into the same molecule, and designs and synthesizes a series of dicarbazole benzothiadiazole compounds through structural modification. Meanwhile, aiming at the defect of narrow spectral response range of the nonmetal organic dye sensitizer, the nonmetal organic dye sensitizer is co-sensitized with the metal dye sensitizer, and the photoelectric conversion efficiency of the DSSCs is expected to be improved while the absorption spectrum range is widened. Disclosure of Invention Aiming at the problems existing in the prior art, the invention aims to provide a biscarbazole benzothiadiazole compound, a preparation method and application thereof. The biscarbazole benzothiadiazole compound can be co-sensitized with a metal dye sensitizer Z907, and the assembled dye sensitized solar cell has better photoelectric conversion efficiency, and adds a new applicable substance for screening a dye sensitizer Z907 co-sensitizer. The invention discloses a biscarbazole benzothiadiazole compound, which comprises the following six structural compounds, wherein the molecular structures are shown in a formula (ZR-2), a formula (ZR-5), a formula (ZR-6), a formula (ZR-7), a formula (ZR-8) or a formula (ZR-9); 。 the invention also discloses a preparation method of the biscarbazole benzothiadiazole compound, which comprises the steps of dissolving a compound shown in a formula (IIa), a formula (IIb), a formula (IIc), a formula (IId), a formula (IIe) and cyanoacetic acid or rhodamine-3-acetic acid in a solvent, adding a base catalyst, heating and refluxing under stirring for reaction, concentrating to remove the solvent after the reaction is finished, dissolving the obtained concentrate in an eluent, separating and purifying the eluent through column chromatography silica gel, collecting the eluent, and steaming the eluent to obtain ZR-2, ZR-5, ZR-6, ZR-7, ZR-8 and ZR-9; The structural formulas of the compounds shown in the formulas (IIa), (IIb), (IIc), (IId) and (IIe) are as follows: 。 further, the invention also discloses that the base catalyst is piperidine. Furthermore, the invention also discloses a catalyst with a mass ratio of 1:6-10, wherein the mass ratio is represented by (IIa), formula (IIb), formula (IIc), formula (IId) or formula (IIe). Further, the invention also discloses a reaction time of 10 h. Furthermore, the invention also discloses a mixed solvent of acetonitrile and chloroform, wherein the volume ratio of the acetonitrile to the chloroform is 2:1. Furthermore, the invention also discloses a mixed solvent of dichloromethane and methanol as an eluent, wherein the volume ratio of the dichloromethane to the methanol is 20:1. Furthermore, the invention also discloses a molar ratio of the compound shown in the formula (IIa), the formula (IIb), the formula (IIc), the formula (IId) or the formula (IIe) to the cyanoacetic acid or the rhodamine-3-acetic acid is 1:5-12. The invention further discloses a compound shown in the formula (IIa), the formula (IIb), the formula (IIc), the formula (IId) or the formula (IIe), wherein the ratio of the amount of the compound to the volume of the solvent is 1:40-75, the unit of the amount of the compound is mmol, and the unit of the volume is mL. Further, the invention also discloses a synthesis method of the compounds shown in the formulas (IIa), (IIb) and (IIc), which comprises the following steps: Dissolving the compounds shown in the formulas (IVa), (IVb) and (IVc) in tetrahydrofuran, adding the tetrahydrofuran into n-hexane solution of n-butyllithium at low temperature, stirring for 1h, adding trimethyl borate, stirring for 15min, stirring overnight at r