对称排列的咔唑基树状分子的合成及其光物理性能和电化学性能.pdf

第 2 1 卷 第 2期 2 0 1 0年 3月 化学 CHEM I CAI 研究 RESEARCH 中国科技核心期刊 h x y j h e n u e d u e ll S y n t he s is a n d Opt ica l a nd Ele ct r o ch e mica l Pr o p e r t ie s o f S y mme t r ica lly Ar r a ng e d Ca r ba z o le De nd r ime r s ZHU Zhi b o CAI YU Chu n Sch o o l 0 Ph ar ma ce u t ical Scie n c e s So u t he r n M e dica l Un iv e r s it y Gu a n g z h o u 5 1 03 1 5 Gu a n gdo n g Chin a Ab s t r a ct One n o ve l ca r b a z o le d e n dr it i c co m p ou nd wa s s yn t he s iz e d by us in g mo di f ie d Ullm a nn co n d e n s a t io n r e a ct io n Th e p r o d u ct wa s ch a r a ct e r iz e d b y me a n s o f n u cle a r ma g n e t ic r e s o n a n ce H NM R C NM R s p e ct r o s co p y a n d t i me o f f li g h t ma s s s p e ct r o me t r y MALDI TOF M a s s At t h e s a me t im e t he lu mine s ce n t p r o p e r t y a nd e le ct r on ic p r o pe r t y o f t he pr o du ct we r e e v a lu a t e d Re s ult s s h ow t ha t t he s y nt h e t i c co mpo un d e x hib it s b lue f lu or e s ce n ce a t a ma x im u m wa v e le ngt h o f 39 4 nm a n d lo w e ne r g y le v e l of hig he s t occu pie d m o le cu la r o r b it a l HOM O a s we l1 Ke y wo r d s ca r b a z o le d e n d r it ic co mp o u n d s y n t h e s is f lu o r e s ce n ce e le ct r o ch e mica l p r o p e r t y CL C n u mb e r O 6 2 6 Do cu me n t co d e A Ar t icle I D 1 0 0 8 一 0 1 2 0 1 0 0 2 0 0 3 8 0 4 对称排列的咔唑基树状分子的合成及其光物理性能 和电化学性能 朱志博 蔡玉春 南方医科大学 药学院 广东 广州 5 1 0 3 1 5 摘 要 采用乌尔曼缩合反应合成了新型的咔唑基 树状分子 利用核磁共 振谱仪 H N MR C N MR 和 飞行 时间质谱 仪 MAI D I TO F Ma s s 对其进行 了表 征 并评价了树状分 子的荧 光性能和 电化学性 能 结果 表明 所 合成 的咔唑基树状化合物在 3 9 4 n m处发蓝光 同时具有低 的 HOMO能级 关键词 咔唑 树状分子 合成 荧光 电化学性能 S y m me t r i ca lly a r r a ng e d d e nd r ime r s wit h mo no d is p e r s e d a n d we ll d e f ine d s t r u ct u r e u s u a lly ha v e in t r i gu in g pr o p e r t ie s a nd ca n b e a pp lie d i n or g a ni c ligh t e m i t t in g d iod e s OI EDs s 7 Th e us e o f co pp e r b r o n z e a nd Pd a s ca t a ly s t s f o r t he U llma nn N a r y la t ion o f ca r ba z o le s b y a r y l ha lid e s m a in ly i od id e s a t hi gh t e m p e r a t u r e s h a s be e n r e p o r t e d e ls e whe r e I n t he pr e s e n t r e s e a r ch we s yn t h e s iz e s y mme t r ica lly a r r a n g e d d e n d r ime r s co n t a in in g e a r b a z o le d e n d r o n a s a d e f i n it e f u n ct i o n a l ch e mica l s t r u ct u r e v ia mo d i f ie d Ullma n n co n d e n s a t io n r e a ct io n s h o wn in S ch e me 1 Th u s n i n e ca r b a z o le d e n dr i m e r s Cz 一 9 we r e s ynt he s i z e d b y u s i ng t he m o d if ie d U llma n n con de ns a t io n r e a ct io n a nd hig he r y ie lds b a s e d o n io d id e s we r e a ch ie v e d t h a n u s in g b a r e co p p e r b r o n z e o r Pd a s t h e ca t a ly s t Th e s y n t h e s iz e d comp ou nd s e x hib it e d blue f lu o r e s ce n ce wit h low ly ing e n e r gy le v e ls o f hig he s t occu pi e d mo le cula r o r bi t a l HOM O R e e e iv e d d a t e 2 0 0 9 一 l 2 0 8 F o u n d a t io n it e m Te ch n o lo g y P r o j e ct o f Gu a n g d o n g P r o v in ce 7 3 0 0 4 4 9 Bio g r a p h y Z HU Zh i b o 1 9 7 5 一 t e a ch in g a s s is t a n t ma s t e r o f s cie n ce ma j o r in g in p h o t o p h y s ica l a n d p h o t o ch e mica l p r o p e r t ie s o f s i na i mo le cu la r o r g a n ic lig h t e mit t i n g ma t e r ia ls C o r r e s p o n d in g a u t h o r E ma il ca r o lin e 9 9 8 8 1 2 6 co n 1 第 2 期 朱志博等 对称排列的咔唑基树状分子的合成及其光物理性能和电化学性能 3 9 一 l I Cz 2 N H V Cz 9 Re a g e n t s a n d co n d it io n s j KI KI Oa AcOH 2 O rain jj Ace0 BFa Et z O l0 min j jj e a r b a z o le Cu 2 O DMF 3 6 h iV K H H2 THF DMS O 2 h V 1 3 5 t r ib r o mo b e n z e n e Cu l l 1 0 一 p h e n a t h r o lin e K 2 C 3 d ime t h y lf o ma mi de DM F 1 6 O f o r 4 8 h 1 Ex pe r im e n t S ch e me 1 S yn t he t ic r o ut e t o de s ir e d Cz 9 d e nd r ime r s I 1 Ch e m ica ls a nd ins t r u me nt A1 l ch e mica ls we r e p u r ch a s e d f r o m Ald r i ch 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o f 5 0 mV s o n a n Aut o la b po t e nt i os t a t PGS TAT 3 0 wit h a t h r e e e le ct r o de s y s t e m pla t i nu m co u nt e r e le c t r o d e g la s s y ca r b o n wo r k in g e le ct r o d e a n d Ag Ag 十 r e f e r e n ce e le ct r o d e 1 mmo l L s o lu t io n o f t he s a mple s in d ich lo r o me t h a ne in t he p r e s e nce o f t e t r a b u t y l a mmo n iu m h e x a f lu o r o p h o s p h a t e n Bu 4 NPG O 1 mo l L a s s u p p o r t i n g e le ct r o ly t e wa s us e d f or t he me a s u r e me n t Th e hig he s t o ccu p ie d mo le cu la r o r b it s l HOM O 一 lo we s t u n o ccu p ie d mo le cula r or b it a l LUM O e ne r g y le ve ls o f Cz 一 9 0 一 矗 0 U g 6 0 0 0 2 4 0 0 0 2 0 0 0 00 3 50 4 00 45 0 50 0 5 5 0 6 00 Wa v ele n gt h U I ll Fig 2 Flu o r e s ce n ce e mis s io n s pe ct r um o f Cz 9 Po t e n t ia l v A g A g V Fig 3 Cy clic v oit a m mog r a m o f Cz 9 i n 0 1 mo l L Bu 4 NP F 6 d ich io r o me t h a n e s o l u t i o n d e n dr ime r s ob t a i ne d by CV a na ly s is a r e s ho wn in Fig 3 I t is s e e n t ha t Cz 一 9 de nd r im e r ha s a n ox id a t i on p o t e nt i a l of 0 7 2 V a nd 1 O 2 V The o ns e t o xi da t io n p ot e nt ia l E o f Cz 一 9 e s t ima t e d f r om t h e f ir s t a no d i c o x id a t i o n wa v e is 0 5 0 V Th e HOM O le v e l o f Cz 一 9 ca lcu la t e d a cco r d in g t o e mp i r i ca l f o r mu la HOMO 一一 E 4 7 1 e V l6 is一 5 2 1 e V An d i t s LUM O le v e l ca lcu la t e d b y s u b t r a ct i n g t h e e n e r g y b a n d ga ps 3 1 5 e V f r o m t he H OM O e ne r gy le v e l is一 2 09 e V The h igh ly in g HOM O e ne r g y le ve l s u g g e s t s t h a t t h e co mp o u n d ma y f in d p o t e n t ia l a p p lica t io n f o r h o le i n j e ct i o n a n d t r a n s p o r t in OLED 0 四 计 0 ll ll0 盘 I 口 f D 第 2期 朱志博等 对称 排列的咔唑基树状分子 的合成 及其光物理性能 和电化 学性能 Re f e r e n ce s 1 He e r b e e k V Ka me r P L e e u w e n V e t a 1 D e n d r i me r s a s s u p p o r t f o r r e co v e r a b l e ca t a l y s t s a n d r e a g e n t s J J C h e m Re v 2 00 2 1 O 2 371 7 37 56 2 At s u s h i K C h o J S Ma s a y o s h i H e t a 1 S y n t h e s i s o f a s y mme t r i ca l ly a r r a n g e d d e n d r i me r s wi t h a ca r b a z o le d e n d r o n a n d a p h e n y la z o me t h i n e d e n d r o n J J Ma cr o mo l 2 0 0 4 3 7 5 5 3 1 5 5 3 7 3 3 X u T H I u R J i n M e t a 1 F a cil e s y n t h e s is o f n o v e lmo n o d i s p e r s e l i n e a r 3 9 l i n k e d o l i g o ca r b a z o le s J J T e t r a h e d r o n Le t t 2 0 05 46 6 88 3 6 8 85 4 F r e d e r i q u e I S e b a s t i a n o C A h me d H e t a 1 D e n d r ime r s m a d e o f p o r p h y r i n co r e s a n d ca r b a z o le ch r o mo p h o r e s a s p e r i p h e r a l u n it s Ab s o r p t i o n s p e ct r a l u mi n e s ce n ce p r o p e r t i e s a n a o x i d a t i o n b e h a v i o r J J Am C h e m S o c 2 0 0 5 1 2 7 1 1 3 5 2 11 3 63 5 Vi n i ch P Mu s u b u I D u o n g r a t ch a n e e k o r n M e t a 1 S y n t h e s is a n d p r o p e r t i e s o f s t a b l e a mo r p h o u s h o le t r a n s p o r t in g m o l e cu le s f o r e le ct r o l u mi n e s ce n t d e v i ce s J J T e t r a h e d r o n L e t t 2 O 0 6 4 7 8 9 4 9 8 9 5 2 6 V in ich P Mu s u b u I T a we e s a k S e t a 1 T h e r ma l ly a n d e l e ct r o ch e mi ca ll y s t a b le a mo r p h o u s h 0 l e t r a n s p o r t in g ma t e r i a ls b a s e d o n ca r b a z o le d e n d r ime r s f o r e l e ct r o lu min e s ce n t d e v i ce s J J T h in S o li d F ilms 2 0 0 8 5 1 6 2 8 8 1 2 8 8 8 7 Xu T H I u R Qi u X P e t a 1 S y n t h e s i s a n d ch a r a ct e r i z a t i o n o f ca r b a z o l e b a s e d d e n d r i me r s w it h p o r p h y r i n co r e s J J Eu r J 0r g C h e m 2 0 0 6 4 O 1 4 4 0 2 0 8 Z h a o Z J X in g Y J Wa n g Z X e t a 1 Du a l f l u o r e s ce n t d o n o ra cce p t o r d y a d w it h t e r ca r b a z o l e d o n o r a n d s wi t ch a b le imi d e a cce p t o r p r o mi s i n g s t r u ct u r e f o r a n in t e g r a t e d l o g i c g a t e J J O r g L e t t 2 0 0 7 9 7 9 9 8 0 4 9 Ta n g R Ta n Z I i Y e t a 1 S y n t h e s i s o f n e w co n j u g a t e d p o l y f lu o r e n e d e r i v a t i v e s b e a r i n g t r ip h e n y la mi n e mo i e t y t h r o u g h a v i n y le n e b r i d g e a n d t h e i r s t a b l e b l u e e l e ct r o lu mi n e s ce n ce J J C h