含BOC保护基团的螺吡喃类化合物的合成及其光致变色性能的研究

合成了5-[N-(叔丁氧甲酰基)氨基]-1,3,3-三甲基-6′-硝基吲哚啉螺吡喃(BOCSPI)和5-[N-(叔丁氧甲酰基)氨基]-1,3,3-三甲基-6′-硝基-8′-甲氧基吲哚啉螺吡喃(BOCSPII)两种光致变色化合物,采用紫外-可见光谱法研究了其在溶液和以不同质量比掺杂在聚甲基丙烯酸甲酯(PMMA)膜中的光致变色性能.研究表明螺吡喃的高掺杂量不利于其开环和闭环态的转化,BOCSPII分子中的甲氧基有利于有色开环体的部花菁的稳定.     

吲哚啉螺吡喃化合物光致变色性能的研究及在生物细胞成像中的应用

吲哚啉螺吡喃是一种重要的光致变色化合物,由于具有良好的变色回复性、抗疲劳性而得到广泛的关注.本文合成了1′-羟乙基-3′,3′-二甲基吲哚啉-6-硝基螺吡喃,研究了该化合物在紫外-可见光交替照射下紫外吸收强度的变化,并测试了光照前后化合物的荧光光谱.在开环态时,化合物具有优良的荧光性能,可以成功应用于细胞成像,在活细胞中可获得清晰的荧光成像图,同时也可以发挥螺吡喃光致变色可循环、耐疲劳等优势.     

光诱导有机化合物异构化反应的研究——Ⅹ. 吲哚啉螺吡喃瞬态吸收光谱的研究

研究了1-正-辛基-3,3-二甲基-吲哚啉-2,2′-螺-5′,6′-(2-溴-4-硝基-苯并)吡喃, 1-正-辛基-3,3-二甲基-吲哚啉-2,2′-螺-5′,6′-(4-硝基-苯并)吡喃, 1-正-辛基-3,3-二甲基-吲哚啉-2,2′-螺-5′,6′-(2,4-二硝基-苯并)吡喃及1-正-辛基-3,3-二甲基-吲哚啉-2,2′螺-5′6′-(2-氯-4-硝基-苯并)吡喃在环已烷和甲苯溶液中光致开环过程的瞬态吸收光谱。观察到具有较长寿命的中间体及聚集体的存在。初步提出异构化反应过程的机制中既包含有三重态过程, 也有单重态参与。     

N-苄基吲(口乃木)啉螺苯并吡喃和螺萘并噁嗪的合成

光致变色物质在数字显示、伪装、装饰及辐射线防护等方面有应用潜力。近年来人们对有机光致变色化合物吲哚啉螺苯并吡喃、螺萘并(口恶)嗪和螺苯并噻喃给予更多的关注。对这些     

新型含氮杂环螺吡喃化合物的合成及性能研究

为了改善螺吡喃的光致变色性能,提高这一系列化合物的耐疲劳度,在螺吡喃吲哚啉环的氮原子上通过短碳链引入含氮杂环基团,成功合成了1'-(3-N-杂环基丙基)-3',3'-二甲基-6-硝基螺[吲哚啉-2,2'(2H)苯并吡喃](4a～4f).这一系列新的化合物.用核磁共振氢谱、碳谱、红外光谱和元素分析对这些化合物进行结构表征.通过紫外吸收光谱研究化合物在不同溶液(乙醇、二氯甲烷和环己烷)中和不同高分子膜(PMMA和PVB)中的变色性质.进一步对化合物4a在不同溶液中的动力学性质,以及在PMMA膜和PVB膜中的热消色动力学性质进行了研究,拟合计算并比较了消色过程的动力学常数.最后,又将化合物4a和不含含氮杂环的螺吡喃母体进行比较,发现耐疲劳度有很大提高.     

苯并螺吡喃吲哚啉-β-环糊精的合成及其性质

近年来,随着超分子化学的发展,环糊精的研究已经成为化学和生物化学领域的热点之一,许多工作都着眼于环糊精进行化学修饰,改变或扩展其对客体分子的识别能力。另一方面,苯并螺吡喃吲哚啉衍生物作为人们熟知的光致变色化合物,其与冠醚相连接,与金属离子的作用及PVC膜性质的研究已有报道,但与环糊精相连接的研究报道极少,本工作首次合成了单－（6－氧－1′－（2－羰乙基）－3′,3′－二甲基－6－硝基螺[2H－苯并吡喃－2,2′－吲哚啉]－β－环糊精（简称为SBI－β－CD）,研究了它的光致变色性质,并利用圆二色谱测定了它对（－）－冰片的包结作用。结果表明,SBI-β－CD具有光敏特性,是一个具有光谱探针的主体化合物。     

6′-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为,其它的则为普通光致变色化合物。同时,结果表明,化合物异构体的稳定性不仅取决于化合物本身的结构,而且还取决于介质环境的影响。     

6'-对位取代苯乙烯基吲哚啉螺吡喃的合成

利用2-亚甲基吲哚啉和取代水杨醛缩合得到十三种新的烷基苯乙烯基吲哚啉螺苯并吡喃。在苯并吡喃部分含有硝基的螺吡喃显示出逆光致变色行为，其它的则为普通光致变色化合物。同时，结果表明，化合物异构体的稳定性不仅取决于化合物本身的结构，而且还取决于介质环境的影响。     

微波法快速合成光致变色螺(口恶)嗪

螺嗪(Ｓｐｉｒｏｘａｚｉｎｅ)是20世纪70年代在螺吡喃基础上发展起来的一类具有良好光致变色性能的化合物,具有很高的抗疲劳性和光稳定性,具有潜在的商业应用前景[1-4],可用作光信息储存材料和光致变色镜片(ＰｈｏｔｏｃｈｒｏｍｉｃＬｅｎｓ)。6 哌啶取代的吲哚啉螺萘并嗪[5-11]相对于未取代的母体化合物具有更优异的光致变色性能,但是文献中的合成方法步骤繁琐、反应时间长、产率较低。本文利用微波合成了6 哌啶基(氰基)吲哚啉螺嗪,合成路线如下:1　实验部分1.1　仪器和试剂显微熔点仪(四川大学科仪厂),温度计未经校正;美国Ｐ…     

聚乙二醇支载的螺吡喃类光致变色化合物的合成及其逆光致变色性质

采用DCC缩合的方法,将吲哚啉螺苯并吡喃的衍生物和聚乙二醇相缩合,以聚乙二醇末端的羟基和吲哚啉螺苯并吡喃衍生物的羧基为反应活性基团,实现了带有羧基的螺吡喃类光致变色化合物支载到了聚乙二醇两端.通过引入亲水基团得到了水溶性较好的螺环类光致变色化合物.通过对产物的紫外-可见光谱的研究发现,产物具有良好的光致变色性质,在乙醇、丙酮和乙酸乙酯中皆具有良好的光致生色现象;产物可溶于水,在紫外光(波长365nm)照射时产生了光消色现象,具有明显的逆光致变色性质.该方法原料易得,反应条件容易控制,为光致变色新材料的研究和开发提供了新方法.     

Preparation of a spirooxazine grafted PMMA and its photochromic properties

A novel spirooxazine (SO) compound was designed and synthesized. Macromolecular materials, called SO-g-hPMMAs (where the g means grafting and the h means partial hydrolysis), were prepared using PMMA (polymethylmethacrylate) with different degrees of hydrolysis. SO-g-5%hPMMA was prepared by reacting SO-containing active C-Br bonds with 5% partially hydrolyzed PMMA. The SO was characterized using ¹H NMR and infrared. Beyond that, photochromic properties were studied in detail. We discuss the effects of hydrochloric acids and hPMMAs of different hydrolysis degrees on photochromic properties of SO-g-hPMMA. Additionally, mechanical properties of the material were studied. Results indicate that the colored ring-opening form (PMC) of SO-g-hPMMA exhibits a good performance in terms of thermal stability, in contrast to the homologous SO. Experiments additionally demonstrate that hydrochloric acid improves the PMC’s thermal stability. SO-g-9%hPMMA demonstrated a good performance of photochromic properties compared to those with different degrees of hydrolysis.     

Structural studies of 1,3-oxazolidine-containing spiropyrans

New 3’-(4-chlorophenyl)-5’,5’-dimethyl-2’-oxospiro[(2H)-chromene-2,4’-1,3-oxazolidine] was synthesized to study the donor influence of the chlorine atom at the N-phenyl substituent on the structure and photochromic properties of 1,3-oxazolidine-containing spiropyrans. Photochemical properties of synthesized 1,3-oxazolidine derivatives were studied at room temperature in toluene. The X-ray diffraction parameters for the new compound were compared with the data obtained earlier for similar spiropyrans.

     

吡啶基二噻吩乙烯轴向配位锰(Ⅱ)-卟啉化合物的合成及性质

针对有机光致变色材料实际应用中存在的光量子产率低,抗疲劳性差,记录信息在读取后遭到破坏等瓶颈问题,本文以2-甲基噻吩为原料,经过卤代、傅克酰基化、Mc Murry环合和Suzuki偶联反应得到的1-(5-氯-2-甲基噻吩-3-基)-2-(5-吡啶基-2-甲基噻吩-3-基)-环戊烯与锰(Ⅱ)-四苯基卟啉反应合成了吡啶基二噻吩乙烯轴向配位锰(Ⅱ)-卟啉化合物,通过紫外可见(UV-Vis)吸收光谱研究了其光致变色性能和抗疲劳性,并结合荧光光谱对无损读取功能进行了探究。实验结果表明,该化合物具有良好的光致变色性能及优良的抗疲劳性,通过波长为254、490和550 nm的光调控可无损地实现信息的写-读-擦过程,该物质有望应用于二进制存储设备中。     

Photochromic Inorganic/Organic Thermoplastic Elastomers

Photochromic materials are an important class of “smart materials” and are broadly utilized in technological devices. However, most photochromic materials reported so far are composed of inorganic compounds that are challenging to process and suffer from poor mechanical performance, severely limiting their applications in various markets. In this paper, inorganic photochromic tungsten trioxide (WO₃) nanocrystals are conveniently grafted with polymers to hurdle the deficiency in processability and mechanical properties. This new type of photochromic material can be thermally processed into desired geometries like disks and dog‐bone specimens. Fully reversible photochromic response under UV light is also achieved for WO₃‐graft polymers, exhibiting tunable response rate, outperforming the pristine WO₃ nanocrystals. Notably, the resulted graft polymers show extraordinary mechanical performance with excellent ductility (≈800% breaking strain) and relatively high breaking strength (≈2 MPa). These discoveries elucidate an effective pathway to design smart inorganic/organic hybrid thermoplastic elastomers endowed with outstanding photochromic and mechanical properties as well as exceptional processability.     

Synthesis and photochromic properties of substituted naphthopyran compounds

A group of 3,3-diaryl-3H-naphtho[2,1-b]pyran compounds with functional substituents at the 5- and 6-positions of the naphthopyran skeleton and the para positions at the 3-aryl moieties were prepared through condensation reactions between 2-naphthol derivatives and 1,1-diarylprop-2-yn-1-ol derivatives. The chemical structures of the compounds were confirmed by NMR and MS. The crystal structure of 3,3-diphenyl-6-morpholino-3H-naphtho[2,1-b]pyran (4b) was determined and the relationship between the pyran substructure and photochromism was discussed. The photochromic properties were studied as well, and decoloration kinetics of colored forms was fitted to the biexponential model. Among these compounds, 4b was considered to be the best one due to the large ΔOD of colored form, which is one of the most important properties used in the photochromic material.     

多功能光致变色化合物

有机光致变色化合物是一种新型有机功能化合物,可广泛应用于光存储、光开关和光转换器件等领域,本文综述近几年来双光致变色化合物体系及具有荧光性能、磁性能等多功能光致变色化合物体系的研究进展,并对有机光致变色化合物的研究应用做了展望。     

DFT/TDDFT Investigation of the Modulation of Photochromic Properties in an Organoboron‐Based Diarylethene by Fluoride Ions

The diarylethene derivative 1,2‐bis‐(5′‐dimesitylboryl‐2′‐methylthieny‐3′‐yl)‐cyclopentene ( 1 ) containing dimesitylboryl groups is an interesting photochromic material. The dimesitylboryl groups can bind to F^?, which tunes the optical and electronic properties of the diarylethene compound. Hence, the diarylethene derivative 1 containing dimesitylboryl groups is sensitive to both light and F^?, and its photochromic properties can be tuned by a fluoride ion. Herein, we studied the substituent effect of dimesitylboron groups on the optical properties of both the closed‐ring and open‐ring isomers of the diarylethene molecule by DFT/TDDFT calculations and found that these methods are reliable for the determination of the lowest singlet excitation energies of diarylethene compounds. The introduction of dimesitylboron groups to the diarylethene compound can elongate its conjugation length and change the excited‐state properties from π→π* transition to a charge‐transfer state. This explains the modulation of photochromic properties through the introduction of dimesitylboron groups. Furthermore, the photochromic properties can be tuned through the binding of F^? to a boron center and the excited state of the diarylethene compound is changed from a charge‐transfer state to a π→π* transition. Hence, a subtle control of the photochromic spectroscopic properties was realized. In addition, the changes of electronic characteristics by the isomerization reaction of diarylethene compounds were also investigated with theoretical calculations. For the model compound 2 without dimesitylboryl groups, the closed‐ring isomer has better hole‐ and electron‐injection abilities, as well as higher charge‐transport rates, than the open‐ring isomer. The introduction of dimesitylboron groups to diarylethene can dramatically improve the charge‐injection and ‐transport abilities. The closed isomer of compound 1 ( 1 C ) has the best hole‐ and electron‐injection abilities, whereas the charge‐transport rates of the open isomer of compound 1 ( 1 O ) are higher than those of 1 C . Importantly, 1 O is an electron‐accepting and ‐transport material. These results show that the diarylethene compound containing dimesitylboryl groups has promising potential to be applied in optoelectronic devices and thus is worth to be further investigated.     

Dielectric permittivity properties of a fulgide dye guest-host liquid crystal

The dielectric permittivity of the nematic liquid crystalline mixture E7, doped with a low concentration of the photochromic material thiophene fulgide, was studied and compared with the properties of the pure E7. Fulgides are a group of thermally stable photochromic materials. On irradiation with ultraviolet light, a ring-closure occurs, giving an isomer which is stable if the dye is kept in the dark. The isomerism induces changes to the steric, dipolar and electronic conjugation properties of the species. A capacitive technique was used to determine the dielectric constants of the fulgide-doped liquid crystalline mixtures. The parallel and perpendicular components of dielectric constant were measured using a single cell, in the latter case in the presence of a magnetic field. Measurements were made on the photochromic system before and after ultraviolet irradiation and a marked variation in the dielectric properties of the mixture was observed. This was shown to be entirely due to the differences in phase transition temperatures between the irradiated and non-irradiated guest-host mixtures.     

Studies on photochromic benzimidazol[1,2a]pyrrolidin-2-ones from the condensation of 2-methyl-3-benzothienylethylidene-(isopropylidene)succinic anhydride with 1,2-diaminobenzenes

Novel photochromic benzimidazol[1,2a]pyrrolidin-2-ones, which give thermally stable highly coloured photochromes, have been synthesised by condensation of 2-methyl-3-benzothienylethylidene(isopropylidene)succinic anhydride with 1,2-diaminobenzene and its 4,5-dimethyl and 4,5-dimethoxy derivatives. The photochromic properties are reported.     

Photochromism of organometallic compounds with structural rearrangement

This article introduces photochromic properties together with structures of organometallic compounds that undergo photo-induced structural rearrangement. The aim of this review is to survey the research on photochromism by using organometallics which possess by their own nature the properties responsible for the photochromism such as bonding and structural fluxionality, electronic state fluctuation, and photochemically active characteristic in both solution and the solid state. Therefore, the organometallics which include the well-characterized organic photochromic moieties, considered to be derivatives of such kinds of organic photochromic compounds, are excluded in this article. Mono-, di-, and poly-nuclear organometallic compounds are presented based on the reaction types such as linkage isomerization, haptotropic rearrangement, and reorganization of metal–ligand and/or metal–metal bonds. Very recently, the crystalline-state photochromism is becoming an attractive field of photochromic chemistry. As a demonstrative example, the photochromism of organometallic rhodium dinuclear complexes having a dithionite ligand (μ-O₂SSO₂), which shows 100% reversible interconversion in the crystalline-state and have been developed in the authors’ laboratory, will be discussed.