新型含环己烯结构的甲基二氮杂萘联苯型聚醚酮的合成及表征

合成了一种新型聚合单体 1 甲基 4,5 二 (4 氯代苯甲酰基 )环己烯 ,并与 4 (3 ,5 二甲基 4 羟基苯基 ) 2 ,3 二氮杂萘 1 酮单体经亲核取代反应 ,成功地合成了含环己烯结构的杂环联苯型聚醚酮聚合物 .用FT IR、1H NMR、DSC、X 射线衍射等方法对聚合物进行了表征 ,并研究了聚合物的溶解性能 .结果表明 ,聚合物是一种具有较高的玻璃化温度的可溶性无规共聚物 .聚合物含有不饱和双键结构 ,是一种反应性高分子     

新型氯取代含杂萘联苯结构可溶性聚芳酰胺的合成、表征和性能

以类双酚单体4-(3-氯-4-羟基-苯基)-2H-二氮杂萘-1-酮(DHPZ-OC)和对氯苯腈为原料进行亲核取代反应合成二腈化合物4-[3-氯-4-(4-氰基苯氧基)苯基]-2-(4-氰基苯基)二氮杂萘-1-酮(),然后在碱性(KOH)条件下进行水解制得了一种新型的含氯取代杂萘联苯结构的芳香二酸,4-[3-氯-4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮().用新二酸与各种芳香二胺进行直接缩合聚合制得了一系列新型氯取代含杂萘联苯结构的聚芳酰胺,特性粘度可达1.23dL/g.用FTIR和¹HNMR研究了新型二酸单体及聚合物的结构.该类聚芳酰胺均可溶解于NMP,DMAc和DMSO等极性有机溶剂中,并且可浇铸成透明韧性膜,其玻璃化转变温度在291～332℃之间,10%的热失重温度在460℃以上.     

Cu（OTf）2催化苄基卤代物与三丁基烯丙基锡的偶联反应

研究了苄基卤代物与三丁基烯丙基锡的偶联反应,当以10mol%Cu(OTf)2为催化剂,CH2Cl2为溶剂时,1-氯甲基-4-苯基萘与三丁基烯丙基锡于室温反应1h,交叉偶联反应产物1-(3-丁烯基)-4-苯基萘(3b)收率即达93%.结果表明,芳环含供电子基的底物反应活性较高,在室温反应几分钟即可完成,而芳环含吸电子基的底物反应活性低.反应产物3b,1-溴-4-(3-丁烯基)萘(3c)和1-(3-丁烯基)-4-硝基萘(3f)未见报道,且其结构经表征确认.     

新型含吡唑基异噁唑衍生物的合成与表征

以查尔酮4和取代的α-氯代吡唑甲醛肟3为原料,通过1,3-偶极环加成反应得到了16种新型的含吡唑基异噁唑衍生物,方法简单可行.化合物4,5-二氢-3-(1-苯基-3-甲基-5-取代-4-基)-5-芳基-4-芳酰基异噁唑啉(5)的结构经过IR,1HNMR,MS及元素分析确证.并利用单晶X射线衍射法测定了5g晶体结构.     

新型联萘衍生物的合成及其光电性能

以咔唑和4,4’-二氨基-1,1’-联萘为初始原料,经重氮化反应、Ullmann反应、NBS亲电取代反应和Suzuki偶联反应,合成了两种新型空穴传输材料——4,4’-双[(9-对甲基苯基)-9H-3-咔唑基]-1,1’-联萘(4a)和4,4’-双[(9-对联苯基)-9H-3-咔唑基]-1,1’-联萘(4b),其结构经1H NMR和元素分析表征。研究了4a和4b在二氯甲烷中的UV和荧光性质。结果表明,4a和4b的最大发射波长分别为429 nm和427 nm。     

含环己烯氮杂环结构的聚醚砜酮三元共聚物合成

用1－甲基－4，5－二（4－氯代苯甲酰基）环己烯与4－（4－羟基苯基）－2，3－二氮杂萘－1－酮、4，4′－二氯二苯砜经亲核共缩聚反应，合成了含环己烯结构的杂环联苯型聚醚砜酮三元共聚物。结果表明，聚合物是一种具有较高的玻璃化转变温度的可溶性无规共聚物。聚合物含有不饱和双键结构，有一种反应性高分子。     

水介质中9,10-二芳基吖啶的洁净合成

水介质中在十二烷基磺酸钠(SDS)催化下, 席夫碱与双甲酮反应合成了一系列9,10-二芳基吖啶衍生物, 同时分离得到一种中间产物. 所有产物的结构通过红外光谱和1H NMR光谱确定, 产物10-(4-氯苯基)-9-(4-甲氧基苯基)-3,3,6,6-四甲基-3,4,6,7,9,10-六氢化吖啶-1,8(2H,5H)-二酮(3i)和中间产物2-{4-氯苯基-[2-(4-甲氧基苯基氨基)-4,4-二甲基-6-氧代环已-1-烯基]甲基}-3-羟基-5,5-二甲基环已-2-烯酮(4h)的结构还通过单晶X射线衍射分析确证.     

含1,3,4-噁二唑环PPV齐聚物的合成及发光特性研究

含有1,3,4-噁二唑结构单元的PPV齐聚物是一类具有良好电子传输功能的发光材料。通过Wittig—Homer反应合成了2,5-二{4-[2-(取代苯基)乙烯基]苯基}-1,3,4-噁二唑(1)。1的化学结构经元素分析和光谱分析确认,其分析数据表明1分子结构中的C=C双键均为反式结构。苯环上的取代基对1的UV—Vis吸收光谱和PL荧光光谱有显著影响。     

新型含环己烯结构的氮杂环聚醚聚合物的合成

用新型聚合单体 1 甲基 4,5 二 (4 氯代苯甲酰基 )环己烯与 4 (4 羟基苯基 ) 2 ,3 二氮杂萘 1 酮、4,4′ 二氯二苯砜单体经亲核共缩聚反应 ,成功地合成了含环己烯结构的杂环联苯型聚醚系列聚合物 .用FT IR、1 H NMR、DSC、X 射线衍射等方法对聚合物进行了表征 ,并研究了聚合物的溶解性能 .结果表明 ,这系列聚合物是具有较高的玻璃化温度的可溶性无规共聚物 .聚合物含有不饱和双键结构 ,可作为交联聚合物、接枝聚合物及其它特种高分子材料的中间体 .而且通过二元或三元聚合 ,来改变交联点和接枝点的密度 ,为进一步得到结构更加多样化与性能各异的聚芳醚的交联聚合物、接枝聚合物及其它特种高分子材料 ,提供一个良好的基础     

异环二取代二茂铁衍生物的合成

从芳基二茂铁的汞化产物中首次分离出四种异环二取代产物 1-氯汞基-1'-芳基二茂铁。1-氯汞基-1'-芳基二茂铁与碘作用得到四种相应的碘代产物。氯汞基二茂铁及1-氯汞基-1'-芳基二茂铁经[ClRh(CO)~2]~2 催化偶联反应制得联二茂铁和三种1'、1''-二芳基联二茂铁。以上化合物的组成与结构经元素分析、IR 和^1H NMR确证, 其中10种为新化合物。     

Synthesis of [3]Rotaxanes that Utilize the Catalytic Activity of a Macrocyclic Phenanthroline–Cu Complex: Remarkable Effect of the Length of the Axle Precursor

[3]Rotaxanes, which consist of one macrocyclic phenanthroline compound and two axle components, were prepared by the oxidative dimerization of an alkyne compound with bulky tris[4′‐cyclohexyl‐(1,1′‐biphenyl)‐4‐yl]methyl blocking group. The catalytic activity of a macrocyclic phenanthroline–Cu complex was utilized to thread the two axle components inside the ring. The alkyne compound with chain of 15 or 20 methylene groups gave [3]rotaxanes in high yields, whereas the axle with a chain of six methylene groups afforded a [3]rotaxane in very poor yield. We also examined the effect of the ring size on the synthesis of [3]rotaxanes. [3]Rotaxanes were not isolated when a macrocyclic phenanthroline compound with a smaller ring size was used.     

Polycyclic aromatic hydrocarbons by ring-closing metathesis

A strategy for the synthesis of polycyclic aromatic hydrocarbons (PAHs) by the ring-closing olefin metathesis (RCM) of pendant olefins on a phenylene backbone has been developed. RCM of 2,4',6',2' '-tetravinyl-[1,1';3',1' ']terphenyl and 2,2',5',2' '-tetravinyl-[1,1';4',1']terphenyl affords in high yield the isomeric [a,j] and [a,h] dibenzanthracenes, respectively. In contrast with other intramolecular annulation methods, such as Friedel-Crafts acylations, this reaction is completely regioselective. Since RCM is reversible and PAHs are often thermodynamic sinks, this strategy is an effective and general method for the preparation of PAHs. Density functional theory calculations support these results. Carbon disulfide is a suitable solvent for these reactions.     

Low-valent vanadium complexes of a pyrrolide-based ligand. Electronic structure of a dimeric V(I) complex with a short and weak metal-metal bond

Deprotonation of the nitrogen atoms of the two pyrrole rings of 1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene with KH followed by further reaction with either VCl 3(THF) 3 or with VCl 2(TMEDA) 2 respectively gave the paramagnetic complexes [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene]VCl(DME) ( 1) and [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene]V(THF) 3 ( 2). Further reduction with the appropriate amount of KH afforded diamagnetic dinuclear [1,3-bis-{[(1'-pyrrol-2-yl)-1,1'-dimethyl]methyl}benzene]V} 2] ( 3). In complex 3, the bridging interaction between the two metal centers is realized via the ligand central benzene ring. Density functional theory calculations have elucidated the nature of the electronic interaction between the two metals with the bridging pi-system thus accounting for its visible structural distortion. Calculations also pointed out the presence of only a weak V-V bond in spite of the short V-V distance.     

Trianionic organoborate triangles

The rigid, angular ligand 3,3,3',3'-tetramethyl-1,1'spirobisindane-5,5',6,6'-tetrol, LH4, in the form of its tetra-anion, L(4-), affords crystalline compounds containing the triangular macrocyclic boron derivative [B3L3](3-) with the counter cations, triethylammonium, imidazolium, tetraethylammonium, and protonated dabco (dabco = 1,4-diazabicyclo[2,2,2]octane). Within a triangular unit all three chiral L(4-) ligands have the same hand although the crystal does contain a racemic mixture of macrocycles. In all four compounds, one out of the three counter-cations per macrocycle is bound inside the macrocycle.     

Synthesis,Structure, and Properties of O6‐Corona[3]arene[3]tetrazines

O₆‐Corona[3]arene[3]tetraazines, a new class of macrocyclic compounds, were synthesized efficiently in a one‐pot reaction from the nucleophilic aromatic substitution reaction between 1,4‐dihydroxybenzene derivatives and 3,6‐dichlorotetrazine in warm acetonitrile. In the crystalline structure, the resulting macrocycles adopt highly symmetric structures of a regular hexagonal cavity with all bridging oxygen atoms and tetrazine rings located on the same plane with phenylene units orthogonally orientated. The constitutional aromatic rings are able to rotate around the macrocyclic annulus, depending on the steric effect of the substituents and temperature, in solution. The electron‐deficient nature revealed by cyclic voltammetry, differential pulse voltammetry, and characteristic absorbances at a visible region show the O₆‐corona[3]arene[3]tetrazines to be suitable macrocyclic receptors for electron‐rich guests.     

Unconventional Kondo effect in redox active single organic macrocyclic transistors

Cyclo[6]- and cyclo[8]pyrrole, two aromatic expanded porphyrins, were studied in a single-molecule transistor (SMT) setup. The analyses of these compounds allowed us to observe an uncommon absence of an even-odd effect in the Kondo resonance in discrete, metal-free organic macrocyclic compounds. The findings from the SMT measurements of these cyclopyrroles were in accord with those from cyclic voltammetry (CV) studies and theoretical analyses. These findings provide support for the notion that SMT measurements could be useful as a tool for the characterization of similar types of aromatic macrocyclic compounds.     

Synthesis,Structure, and Properties of O6‐Corona[3]arene[3]tetrazines

O₆‐Corona[3]arene[3]tetraazines, a new class of macrocyclic compounds, were synthesized efficiently in a one‐pot reaction from the nucleophilic aromatic substitution reaction between 1,4‐dihydroxybenzene derivatives and 3,6‐dichlorotetrazine in warm acetonitrile. In the crystalline structure, the resulting macrocycles adopt highly symmetric structures of a regular hexagonal cavity with all bridging oxygen atoms and tetrazine rings located on the same plane with phenylene units orthogonally orientated. The constitutional aromatic rings are able to rotate around the macrocyclic annulus, depending on the steric effect of the substituents and temperature, in solution. The electron‐deficient nature revealed by cyclic voltammetry, differential pulse voltammetry, and characteristic absorbances at a visible region show the O₆‐corona[3]arene[3]tetrazines to be suitable macrocyclic receptors for electron‐rich guests.     

Naphth[4]arene: Synthesis,Conformations, and Application in Color-Tunable Supramolecular Crystalline Assemblies

Although the chemistry of macrocyclic arenes has seen rapid development in recent years, the synthesis of new macrocyclic arenes from aromatic rings with no directing groups remains a challenge. In this work, a new macrocyclic arene, naphth[4]arene (NA[4]A), composed of four naphthalene rings bridged by methylene groups, was synthesized using macrocycle-to-macrocycle conversion. NA[4]A shows 1,3-alternate and 1,2-alternate conformations in the solid state, which can be selectively obtained. By supramolecular co-assembly of NA[4]A and 1,2,4,5-tetracyanobenzene (TCNB) in different concentrations and temperatures, two conformation-dependent crystalline luminescent co-assemblies 1,2-NTC and 1,3-NTC can be selectively prepared. Interestingly, the two charge-transfer crystalline assemblies containing NA[4]A with different conformations show bright yellow and green fluorescence, and also display high photoluminescence quantum yields (PLQYs) of 45 % and 43 %. Furthermore, they exhibit color-tunable two-photon excited upconversion emission.     

Efficient functionalizations of heteroatom-bridged calix[2]arene[2]triazines on the larger rim

Heteroatom-bridged dichlorinated calix[2]arene[2]triazines, which were synthesized from the fragment coupling reactions of cyanuric chloride and various aromatic dinucleophiles, are a unique type of platform for the construction of functional macrocyclic host molecules. Utilizing a very convenient and straightforward nucleophilic displacement reaction of dichlorinated tetraoxacalix[2]arene[2]triazine by various chelating group-containing amines, a number of functionalized tetraoxacalix[2]arene[2]triazines on the larger rim were efficiently synthesized in good yields. The resulting tetraoxacalix[2]arene[2]triazines armed with two 2,2'-bi(pyridinyl)amino or two bis(2-pyridinemethyl)amino groups selectively formed 1:1 complexes with Cu2+ ion through most probably a chelating interaction effect.     

Synthesis of rccc- and rctt-diastereoisomers of novel triazole-containing calix[4]resorcinols

Novel calix[4]resorcinols containing four triazole fragments on the aromatic substituents of the calixarene framework were synthesized via a one-step condensation of resorcinol and its derivatives with 4-(1-benzyl-1H-[1,2,3]triazol-4-ylmethoxy)benzaldehyde. The macrocyclic products are rctt- and/or rccc-isomers, which were isolated and characterized by NMR and single crystal X-ray diffraction studies. The same products were also prepared via the click-reaction of benzyl azide with previously synthesized calix[4]resorcinols containing four alkyne terminal groups on the aromatic substituents. In this case, only rctt-diastereomers of the corresponding calixarenes were isolated, which is governed by conformational features of the starting macrocycles.