阅读说明：本技术 一种光致电子转移超分子纳米粒子的制备方法及应用 (Preparation method and application of photoinduced electron transfer supramolecular nanoparticles ) 是由 刘国星 崔天巍 于 2019-09-30 设计创作，主要内容包括：一种光致电子转移超分子纳米粒子,其构筑单元以三联吡啶钌(2+)修饰的柱[5]芳烃为主体,以戊腈修饰的三芳胺作为客体,通过主-客体络合作用构筑纳米超分子组装体；其制备方法是将三联吡啶钌(2+)修饰的柱[5]芳烃和戊腈修饰的三芳胺以3:2化学计量比配成溶液,并均匀地混合。本发明的优点是：该光致电子转移超分子纳米粒子制备方法简单,用量少,具有较高的光致电子转移效率,且该光致电子转移过程可被竞争性客体所调节,实现可控的光致电子转移,在发展可控的、高效的太阳能电池、光动力治疗材料、光催化剂领域具有广阔的应用前景。(A photoinduced electron transfer supermolecule nano particle is characterized in that a building unit takes terpyridyl ruthenium (2+) modified column [5] arene as a main body, triarylamine modified by valeronitrile as an object, and a nanometer supermolecule assembly is built through the host-object complexation; the preparation method comprises the steps of preparing a solution from terpyridyl ruthenium (2+) modified column [5] arene and valeronitrile modified triarylamine according to the stoichiometric ratio of 3:2, and uniformly mixing. The invention has the advantages that: the photoinduced electron transfer supermolecule nano particle has the advantages of simple preparation method, small using amount and higher photoinduced electron transfer efficiency, and the photoinduced electron transfer process can be regulated by competitive objects to realize controllable photoinduced electron transfer, thereby having wide application prospect in the fields of developing controllable and efficient solar cells, photodynamic therapy materials and photocatalysts.)

1. A photo-induced electron transfer supramolecular nanoparticle, comprising: the construction unit of the photoinduced electron transfer supramolecular nano particle takes terpyridyl ruthenium (+2) modified column [5] arene as a main body, takes valeronitrile modified triarylamine as an object, and constructs a nano supramolecular assembly through the host-object complexation, wherein the main body is shown as a formula I, and the construction unit of the object is shown as a formula II:

2. The method for preparing photo-induced electron transfer supramolecular nanoparticles as claimed in claim 1, wherein: dissolving terpyridyl ruthenium (2+) modified column [5] arene and valeronitrile modified triarylamine in chloroform, and uniformly mixing to prepare a solution of supramolecular nanoparticles, wherein the mass ratio of the terpyridyl ruthenium (2+) modified column [5] arene to the valeronitrile modified triarylamine is 3:2, the concentration of the ruthenium terpyridyl (2+) modified column [5] arene is 1 multiplied by 10 < -5 > mol/L.

3. The method for preparing photo-induced electron transfer supramolecular nanoparticles according to claim 2, characterized in that: the preparation method of the terpyridyl ruthenium (2+) modified column [5] arene comprises the following steps: adding 0.28mmol of terpyridine modified column [5] arene and 0.12mmol of Ru (DMSO)4Cl2 into a reaction tube under the protection of nitrogen, adding ethanol and N, N-dimethylformamide, refluxing and stirring the mixed solution for 24 hours, cooling to room temperature, adding diethyl ether, separating out solids, filtering to obtain a filter cake, dissolving the filter cake into dichloromethane, adding a saturated ammonium hexafluorophosphate solution, stirring overnight, filtering the formed solids, washing the filter cake with water and ethanol, and eluting the crude product with an eluent dichloromethane: separating methanol at 100:1 through a column to obtain the terpyridyl ruthenium (2+) modified column [5] arene.

4. The method for preparing photo-induced electron transfer supramolecular nanoparticles according to claim 2, characterized in that: the preparation method of the triarylamine modified by valeronitrile comprises the following steps: under the protection of nitrogen, 0.95mmol of alkynyl-modified triphenylamine, 5.67mmol of azidovaleronitrile and 5.67mmol of cuprous iodide are respectively added into N, N-dimethylformamide, reacted at 70-90 ℃ for 48 hours, after cooling to room temperature, the cuprous iodide is filtered off with celite, the filtrate is extracted with dichloromethane and water, the organic layer is dried over anhydrous sodium sulfate and subsequently evaporated to dryness, and the crude product is eluted with dichloromethane: separating methanol by a 60:1 column chromatography to obtain the triarylamine modified by the valeronitrile.

5. The photo-induced electron transfer supramolecular nanoparticles as claimed in claim 1, applied to the construction of controllable optoelectronic materials.

Technical Field

The invention belongs to the technical field of nano supermolecule materials, and particularly relates to a preparation method and application of controllable photoinduced electron transfer nanoparticles.

Background

The Photoinduced Electron Transfer (PET) reaction is a very important process in nature and in the field of science and technology, and is widely applied to solar energy conversion, photocatalysis, synthetic organic photoreaction, ultrahigh resolution imaging, photodynamic therapy and the like, as follows: (1) m.k.brennaman, r.j.dillon, l.alibabaei, m.k.gish, c.j.dares, d.l.ashford, r.l.house, g.j.meyer, j.m.papanikoas, t.j.meyer, j.am.chem.soc.2016,138, 13085-13102; (2) m.r.gill, j.a.thomas, chem.soc.rev.2012,41, 3179-; (3) huang, B.Yu, P.Zhang, J.Huang, Y.Chen, G.Gasser, L.Ji, H.Chao, Angew.Chem.Int.Ed.2015,54, 14049. 14052.(4) R.F.Lane, G.S.Kaminski Schierle, S.van de Linde, C.F.Kaminski, Methods appl.Fluoresc.2016,4,022004, (5) D.L.Ashford, M.K.Gish, A.K.Vannucci, M.K.Brennaman, J.L.Templex, J.M.Papanolas, T.J.yer, chem.Rev.49, 115,13006-13049 (6) N.Zhang, J.Huang.2015.2015.31, Roche-16. electronic transfer efficiency, and the like do not have serious effects on the electronic transfer efficiency of conventional systems, such as Nissum.Rev.Chem.16, Roche, Reye, Roche, and others. Therefore, the development of controllable photoinduced electron transfer systems is a very important research topic.

In recent years, supramolecular self-assembly by host-guest complexation has become the focus of research. This non-covalent interaction has the advantage of being simple and controllable, and the development of controllable self-healing materials, energy-transfer light-trapping devices, drug-controlled-release, photo-electron transfer materials, etc. has entered the research field of supramolecular chemists and materials chemists, see (1) h.chen, x.ma, s.wu, h.tie, angelw.chem.int.ed.2014, 53,14149 14152.(2) j.li, y.chen, j.yu, n.cheng, y.liu, adv.mater.2017,29,1701905.(3) s.ikejiri, y.takashima, m.osaki, h.yamaguchi, a.harada, j.am.chem.2018, 140,17308-17315.(4) d.guo, k.wang, wang.wang, wang.wa, wa, j.35, g.201, r.22. t.22. kayashi, r.22. kayashi, j.12. am.12. chem.12. wo, r.22. u, r.22. 7, r.g.r.g. 7, r.g. 7, g. 1, g. 9, g. h.g. chen, g. chen, r, g. h.35, g. h.g. 9, g. chen, g. h.35, g. h.g. 9, g. chen, g. 9, g. h.35, g. 7, g. chen, g. 7, g. 9, g. chen, the fifth generation macrocyclic body, emerging after calixarenes, was studied as it appeared as spring shoots after rain. The research work for constructing the photoinduced electron transfer by using the pillar arene as a medium has great innovation, see M.Fathrala, N.L.Strutt, S.Sampath, K.Katsiev, K.J.Hart-lieb, O.M.Bakr, J.F.Stoddart, chem.Commun.2015,51, 10455-10458. Therefore, the construction of a high-efficiency and controllable photoinduced electron transfer system is an innovative research subject and has very important practical application value for the development of controllable solar cells and photodynamic therapy materials.

Disclosure of Invention

The invention aims to provide a preparation method and application of photoinduced electron transfer nanoparticles aiming at the technical problems of low photoinduced electron transfer efficiency and uncontrollable, wherein a supramolecular nano system is based on an electron-rich triarylamine derivative and electron-deficient terpyridyl ruthenium (+2) modified column [5] arene which are mutually interwoven to form regular nanoparticles through a main-guest complexation, the triarylamine has stronger electron donating capability and the terpyridyl ruthenium (+2) has strong electron accepting capability, the difference between HOMO and HOMO orbitals is increased, and the photoinduced electron transfer efficiency is improved; and simultaneously, the coupling through the non-covalent action of supermolecule provides possibility for a controllable photoinduced electron transfer process.

the technical scheme of the invention is as follows:

A photoinduced electron transfer supramolecular nanoparticle is characterized in that a column [5] arene modified by terpyridyl ruthenium (+2) is used as a main body, triarylamine modified by valeronitrile is used as an object, and a nano supramolecular assembly is constructed through the host-object complexation, wherein the main body is shown as a formula I, and the construction unit of the object is shown as a formula II:

The preparation method of the photoinduced electron transfer supramolecular nanoparticles comprises the steps of dissolving terpyridyl ruthenium (2+) modified column [5] arene and valeronitrile modified triarylamine in chloroform, and uniformly mixing to prepare a supramolecular nanoparticle solution, wherein the mass ratio of the terpyridyl ruthenium (2+) modified column [5] arene to the valeronitrile modified triarylamine is 3:2, the concentration of the ruthenium terpyridyl (2+) modified column [5] arene is 1 multiplied by 10 < -5 > mol/L.

The preparation method of the terpyridyl ruthenium (2+) modified column [5] arene comprises the following steps: adding 0.28mmol of terpyridine modified column [5] arene and 0.12mmol of Ru (DMSO)4Cl2 into a reaction tube under the protection of nitrogen, adding ethanol and N, N-dimethylformamide, refluxing and stirring the mixed solution for 24 hours, cooling to room temperature, adding diethyl ether, separating out solids, filtering to obtain a filter cake, dissolving the filter cake into dichloromethane, adding a saturated ammonium hexafluorophosphate solution, stirring overnight, filtering the formed solids, washing the filter cake with water and ethanol, and eluting the crude product with an eluent dichloromethane: separating methanol at 100:1 through a column to obtain the terpyridyl ruthenium (2+) modified column [5] arene.

The preparation method of the triarylamine modified by valeronitrile comprises the following steps: under the protection of nitrogen, 0.95mmol of alkynyl-modified triphenylamine, 5.67mmol of azidovaleronitrile and 5.67mmol of cuprous iodide are respectively added into N, N-dimethylformamide, reacted at 70-90 ℃ for 48 hours, after cooling to room temperature, the cuprous iodide is filtered off with celite, the filtrate is extracted with dichloromethane and water, the organic layer is dried over anhydrous sodium sulfate and subsequently evaporated to dryness, and the crude product is eluted with dichloromethane: separating methanol by a 60:1 column chromatography to obtain the triarylamine modified by the valeronitrile.

The photoinduced electron transfer supramolecular nanoparticles are applied to the construction of controllable photoelectric materials.

The invention has the advantages that: the photoinduced electron transfer supramolecular nanoparticles constructed by supramolecular assembly of the column [5] arene modified by terpyridyl ruthenium (2+) and the triarylamine modified by valeronitrile are simple and convenient in preparation method, the use amount of main and object raw materials is small, the fluorescence quenching efficiency of the electron donor triarylamine can be known to have higher photoinduced electron transfer efficiency, and the nanoparticles refer to Chengdong, Peak, Chengdong, Wangrui, Yangyuan, the proceedings of the combined fertilizer industry university, 2009,32, 1094-; zhang hong, Zhanhua, Shentao, China science (edition B), 1997,27, 158-. The controllable photoinduced electron transfer performance of the nano supermolecular assembly is endowed through the host-guest action between the columnar aromatic hydrocarbon and the triazole valeronitrile; the photoinduced electron transfer supramolecular nanoparticles have very important significance for developing controllable solar cells, photodynamic therapy materials and supramolecular photocatalysts, and have very great application prospects.

Drawings

FIG. 1 shows NMR spectra of ruthenium terpyridyl (2+) modified column [5] arene.

FIG. 2 shows the NMR spectrum of a triarylamine modified with valeronitrile.

FIG. 3 is a comparison graph of NMR hydrogen spectra of ruthenium (2+) terpyridyl [5] arene and triarylamine modified by valeronitrile, (a) is a partial NMR hydrogen spectrum of ruthenium (2+) terpyridyl [5] arene, (b) is a partial NMR hydrogen spectrum of a nano supermolecule assembly formed by mixing ruthenium (2+) terpyridyl [5] arene and triarylamine modified by valeronitrile in a ratio of 3:2, and (c) is a partial NMR hydrogen spectrum of triarylamine modified by valeronitrile

FIG. 4 is a schematic drawing of a nano-morphology formed by an assembly formed by mixing terpyridyl ruthenium (2+) modified column [5] arene and valeronitrile modified triarylamine in a ratio of 3 to 2, (a) a schematic drawing of a transmission electron microscope of the assembly, and (b) a schematic drawing of a scanning electron microscope of the assembly.

FIG. 5 shows the UV-VIS absorption spectrum of an assembly formed by a terpyridyl ruthenium (2+) modified column [5] arene, a terpyridyl ruthenium (2+) modified column [5] arene and a valeronitrile modified triarylamine.

FIG. 6 shows the fluorescence emission spectrum of column [5] arene modified with terpyridyl ruthenium (2+) continuously added to triarylamine modified with valeronitrile.

FIG. 7 shows fluorescence emission spectra of adiponitrile continuously added to an assembly of terpyridyl ruthenium (2+) modified column [5] arene and valeronitrile modified triarylamine.

Detailed Description