N,N′-双(3-吡啶醛)-(1R,2R)-环己二胺席夫碱Ag(Ⅰ)配合物的合成、结构和荧光性质研究.pdf

第 3 0卷第 1 0期 2 0 1 4年 1 0月 无 机 化 学 学 报 CHI NE S E J 0URN AL 0F I N0RG AN I C C HEMI S T RY V0 l 3 0 No 1 0 2 4 3 3 2 4 3 9 N 双 3 吡啶醛 1 R 2 R 环 己二胺 席夫碱 A g I 配合物的合成 结构和荧光性质研究 张奇龙 1 冯广卫 胡 鹏 1 朱必学2 贵阳医学院化学教研 室 贵 阳 5 5 0 0 0 4 2 贵州省大环化学及超分子化学重点实验室 贵阳5 5 0 0 2 5 摘 要 以 3 吡啶醛 和 1 2 R 环己二胺进行缩合得 到 S ch i ff碱配体 L 然后 用配体 L 和 A g N O 进行配位反应 得 到配合物 A g L N O3 1 并用元素分析 F T I R X 射线单晶衍射 热重分析 粉末衍射对其进行了表征 晶体结构表明 配合物 1属于单斜 晶系 c2 空间群 A g I 的配位环境均为扭曲四面体 分别和硝酸根的氧原子 配体中的2 个吡啶氮原子以及 1 个亚胺氮原子配 位 配体 L 有 2种配位模式 其中 1 个配体用两臂的 2个毗啶氮原子分别和2个 A g I 离子配位 另外 1 个配体用两臂的 2个 吡啶氮原子分别和2 个A g I 离子配位 同时2 个亚胺氮原子也分别和2 个A g I 离子配位 这样配合物形成3 D孔状结构 同时 研究 了配合物 的固体荧光性质 关键词 席夫碱 A I 配合 物 晶体结构 荧光性质 中图分类号 0 6 1 4 1 2 2 文献标识码 A 文章编号 1 0 0 1 4 8 6 1 2 0 1 4 1 0 2 4 3 3 0 7 DoI 1 0 1 1 8 6 2 C J I C 2 0 1 4 3 3 4 S y n t h e s is C r y s t a l S t r u ct u r e a n d F lu o r e s ce n ce P r o p e r t y o f Ag I C o mp l e x wi t h S ch i ff Ba s e B i s 3 p y r i d i n e ca r b 0 x a l d e h y d e 1 R 2 R cy cl o h e x a n e d i imi n e L i g a n d Z HA N G Q i L o n g F E NG G u a n g We i HU P e n g Z HU B i X u e D e p a r t m e n t o f C h e m i s t r y G u i y a n g Me d i ca l C o ll e g e G u ang 5 5 0 0 0 4 C h in a e K e la b o r a t o ry o f Ma cr o cy cl e a n d S u p r a mo l e cu l a r C h e m i s t r y G u a n g 5 5 0 0 2 5 C h i n a A b s t r a ct T h e S ch iff b a s e li g a n d L N 一 b is 3 一 p y r i d in e ca r b o x a ld e h y d e 一 1 R 2 R cy c1 o h e x a n e d iimi n e w a s s y n t h e s iz e d f r o m t h e co n d e n s a t io n r e a ct i o n o f 1 R 2 R 1 2 cy cl0 h e x a n e d ia min e w it h 3 p y r id in e ca r b o x a ld e h y d e A g N 0 3 r e a ct e d w i t h L t o g iv e t h e co mp le x A g L N 0 3 1 w h ich w a s ch a r a ct e riz e d b y e le m e n t a l a n a ly s is F T I R s in g le cr y s t a l X r a y d if f r a ct io n t h e r m o g r a v ime t r ie A n a ly s is T G A a n d p o w d e r X r a y d if f r a ct io n I n t h e co mp le x t h e co o r d i n a t io n e n v ir o n me n t o f A g I a d o p t e d a d is t o r t e d t e t r a h e d r a l g e o m e t ry b e i n g b o u n d t o o n e o x y g e n d o n o r f r o m a mo n o d e n t a t e n it r a t e a n io n a s w e ll a s t o n it r o g e n a t o ms a n d i min e n it r o g e n a t o ms fro m t h r e e a d j a ce n t mo le cu le s o f L I n co m p o u n d 1 t h e L lig a n d s co o r d in a t e d t o t h e A g I io n s in t w o d if f e r e n t w a y s T h e fir s t in v o lv e d L b r id g in g o f A g I ce n t e r s in a b id e n t a t e f a s h io n v ia t h e t w o t e r m in a l p y r id y l N d o n o r s o n ly T h e o t h e r b in d in g m o d e in v o lv e d L co o r d in a t io n t o A g I i o n s in a t e t r a d e n t a t e mo d e t h r o u g h b o t h t e r min a l p y ri d y l N d o n o r s a n d b o t h a min e n it r o g e n a t o ms I n t h is mo d e t h e co mp le x 3 D p o r o u s s t r u ct u r e o f 1 wa s f o rm e d At t h e s a me t ime t h e fl u o r e s ce n t p r o p e rtie s o f lig a n d a n d co mp le x 1 a r e in v e s t ig a t e d in t h e s o lid s t a t e a t r o o m t e mpe r a t u r e CCDC 9 6 9 69 9 L 9 69 7 0 0 1 K e y w o r d s S ch i ff b a s e Ag I co mp le x cr y s t a l s t r u ct u r e flu o r e s ce n t p r o p e r t y 收稿 日期 2 0 1 4 0 3 1 4 收修改稿 日期 2 0 1 4 0 4 2 8 国家 自然科学 基金 N o 2 1 0 6 1 0 0 3 贵州省联合基金 黔科合 L G字 2 O 1 2 O l 6 资助项 目 通 讯联 系人 E m a i l g z u q l z h a n g 1 2 6 co m 2 4 3 4 无机化学学报 第 3 0卷 0 I n t r o d uct io n A g r e a t n u mb e r o f co o r d in a t io n p o ly me r s co n s t r u ct e d b y S ch iff b a s e lig a n d s a n d t r a n s it io n me t a l s a lt s h a v e b e e n e x t e n s iv e ly s t u d ie d d u e t o t h e f a ct t h a t S ch iff b a s e lig a n d s h a v e t h e g r e a t fl e x ib ilit y in t h e s y n t h e s is a n d g o o d co o r d i n a t io n a b ilit y t T h e s t ruct u r a l d i v e r s it y o f t h e s e ma t e ri a ls d e r iv e s f r o m ma n y f a ct o r s s u ch a s t h e me t al io n t h e t e mp la t e t h e me t a l t o l ig a n d r a t i o t h e p H v a lu e t h e co u n t e r a n io n a n d t h e n u mb e r o f co o r d in a t io n s it e s p r o v id e d b y t h e o r g a n ic lig a n d s An i o n s b e in g a p e r ma n e n t p a r t o f t h e fin a l p r o d u ct ca n in fl u e n ce t h e s t r u ct u r e d ir e ct ly b y co o r d in a t in g t o t h e me t a l io n s o r b y a ct in g a s t e mp la t e s t o in d u ce s e lf a s s e mb ly t 堋 T h e r e f o r e f u lly in co r p o r a t in g d if f e r e n t co u n t e r a n io n s ma y ca u s e s ig n ifi ca n t s t r u ct u r a l ch a n g e s in t h e r e s u lt a n t p o l y me r s S ilv e r I io n s p la y a ce n t r a l r o le i n t h e f o r mu la t io n o f s u ch o r g a n ic in o r g a n ic h y b r id a s s e mb l ie s a s s o f t a cid s t h e y f a v o r s t a b le co o r d in a t io n t o s o ft b a s e s s u ch a s l ig a n d s t h a t co n t a in s u lf u r a n d u n s a t u r a t e d n it r o g e n a t o ms Amo n g o f t h e s e MOF ma t e r ia ls b id e n t a t e N co n t a in in g h e t e r o cy clic lig a n d s f o r t h e co n s t ruct io n o f s o me u n iq u e p o r o u s a s s e mb lie s h a v e b e e n d e s ig n e d a n d s y n t h e s i z e d a n d t h e ir p o t e n t ia l a p p lica t io n s a r e n o w w e ll d o cu me n t e d f J 5 I Ho we v e r t h e u s e o f ch ir a l d ia min e s s u ch a s t r a n s 一 1 R 2 R 1 2 一 cy cl o h e x a n e d ia min e fo r t h e s y n t h e s is o f ch i r a l S ch iff b a s e lig a n d s d e ri v e d f r o m p y r id in e ca r b o x a ld e h v d e s h a s n o t r e ce iv e d mu ch a t t e n t io n 6 1 8 1 I n a r e ce n t s t u d y w e in v e s t ig a t e d t h e in t e r a ct io n o f L S ch e me 1 w it h A g C F 3 S O 3 a n d f o u n d t h a t t h e p r o d u ct co m p l e x A g L 2 C F 3 S 0 3 4 H 2 0 e x is t e d a s a 4 4 co n n e ct e d t w o d im e n s io n a l 2 D s h e e t w it h a co r r u g a t e d s ur f a ce 瑚 I n t his a rticle we r e p o r t t h e s y n t h e s is s t ruct u r a l ch a r a ct e r iz a t io n a n d t h e r ma I L OR 2 R S ch e me 1 S ch e ma t ic d r a w in g o f lig a n d L b e h a v io r o f t h e co mp le x r e s u lt in g fro m t h e in t e r a ct io n o f t h e 1 R 2 R N N 一 b is 4 p y r id y 1 id e n e d ia m in o cy clo h e x a n e lig a n d L w it h A g N O 3 1 Ex p e r ime nt a l 1 1 M at e r ia ls a nd m e a s ur e m e nt s A1 l che mica ls f r o m co mme r cia l s o u r ce s we r e o f r e a g e n t g r a d e a n d u s e d w it h o u t p u r i fi ca t io n E le me n t a l C H N a n a l y s is d a t a w e r e o b t a i n e d w it h a V a r io E L m e le me n t a l a n a ly z e r I R s p e ct r a we r e r e co r d e d b v K B r p e lle t s o n B io R a d F T I R s p e t r o p h o t o me t e r in t h e 4 0 0 4 0 0 0 cm一 r a n g e 1 H N MR s p e ct r a w e r e r e co r d e d o n a J EOL E C X 5 0 0 MHz s p e ct r o me t e r u s in g CDC 1 3 s o lu t io n a t r o o m t e mpe r a t u r e Th e r mo g r a v ime t r ic me a s u r e me n t s we r e ca r r ie d o u t in a ni t r o g e n s t r e a m u s in g a Ne t z s ch S T A4 4 9 C a p p a r a t u s wit h a h e a t in g r a t e o f 1 0 cI min X R a y p o w d e r d if f r a ct io n XR P D wa s ca ie d o u t o n a RI GAKU DMAX2 5 0 0 a p p a r a t u s 1 2 S y n t h e s is o f the lig a n d L 1 R 2 R d ia m in o cy clo h e x a n e 1 1 4 g 1 0 mm o 1 a n d 3 f o r my l p y r id i n e 2 1 4 g 2 0 m mo 1 in a 1 2 m o la r r a t io w e r e d is s o lv e d i n 1 0 0 mL o f a n h y d r o u s me t h a n o 1 T h e r e a ct i o n mi x t u r e wa s r e fl u x e d for 6 8 h wh ils t ma in t a i n in g d r y co n d it io n s T h e r e s u lt in g s o lu t io n w a s t h e n e v a p o r a t e d u n d e r r e d u ce d p r e s s u r e t o o b t a in a li g ht y e ll o w s e mis o lid which o n r e cr y s t al liz a t io n f r o m d ie t h y l e t h e r g a v e a w h i t e s o lid Yie ld 2 0 5 g 7 0 H N MR C D C 1 3 T MS 6 8 7 3 s 2 H p y r i d y 1 8 5 6 s 2 H p y r id y 1 8 2 2 s 2 H 一 C H N 7 9 4 s 2 H p y r id y 1 7 2 5 m 2 H p y r i d y 1 3 4 4 s 2 H ch ir a 1 H 1 5 0 1 9 0 m 8 H C H2 A n a 1 C a lcd for C l 8 H2 0 N 4 C 7 3 9 4 H 6 8 9 N 1 9 1 6 F o u n d C 7 4 0 8 H 6 7 7 N 1 9 2 0 F T I R K B r p e lle t a m 3 4 3 2 w 3 1 2 9 s 2 9 3 4 m 1 6 4 2 m 1 4 0 1 m 1 3 2 6 w 1 1 9 1 w 1 0 2 6 w 8 1 9 w 7 0 6 w 1 3 S y n t h e s is o f Ag C 1 J I NOs A g N 0 3 0 1 7 g 1 mm o 1 in e t h a n o l 2 0 mE w a s a d d e d d r o p w is e w i t h s t i i n g t o L 0 2 9 2 g 1 m mo 1 in e t h a n o l 1 0 mE a n d s t iF in g w a s co n t in u e d a t r o o m t e mp e r a t u r e for 2 h Th e n t h e r e a ct io n mix t u r e wa s k e p t in a r e f ri g e r a t o r o v e r n ig h t A wh it e a mo r ph o u s s o li d s e p a r a t e d o u t T h e s o lid wa s co lle ct e d b y fi lt r a t io n wa s h e d w it h a f e w d r o p s o f me t h a n o l a n d 第 1 0期 张奇龙 等 一 双 3 一 吡啶醛 一 1 R 2 R 一 环 己二胺席夫碱 A g I 配合物 的合成 结构 和荧光性质研究 2 4 3 5 d r ie d a t r o o m t e mp e r a t u r e t o g i v e 1 a s a wh it e s o lid in 4 3 y i e ld T h e s o lid wa s d is s o lv e d in e x ce s s e t h a n o l a t r o o m t e mp e r a t u r e a n d s lo w e v a p o r a t io n o f t h is s o lu t io n y ie ld e d co lo r le s s b lo ck s h a p e d s in g le cr y s t a ls t h a t p r o v e d s u it a b le f o r X r a y a n a l y s is F T I R K B r p e lle t cm 3 4 5 9 m 2 9 2 8 w 2 8 5 6 w 1 6 3 5 m 1 3 8 2 s 1 2 9 8 w 1 1 1 8 9 w 1 1 lO w 1 1 3 0 w 9 3 4 w 7 0 3 w 6 3 1 w An a 1 C a le d for C l8 H2 o A g N 5 0 3 C 4 6 7 7 H 4 3 6 N 1 5 1 5 F o u n d C 4 6 7 1 H 4 45 N 1 5 2 2 1 4 X r ay cr y s t allo g r a phic s t ud y X r a y d if f r a ct io n d a t a we r e co lle ct e d a t r o o m t e mp e r a t u r e wit h g r a p h it e mo n o ch r o ma t e d Mo Ka r a d ia t io n o n B r u k e r S ma r t Ap e x s in g le cr y s t a l d if f r a c t o me t e r b y u s in g a p s ca n me t h o d Un it ce ll d ime n s io n s w e r e o b t a in e d w it h le a s t s q u a r e s r e fi n e me n t s a n d mu lt i s ca n a b s o r p t io n co r r e ct io n s we r e a p p l ie d b y T a b le 1 Cr y s t a llo g r a p h ic u s in g S ADAB S p r o g r a m T h e s t r u ct u r e s we r e s o lv e d b y d i r e ct me t h o d s u s in g t h e p r o g r a m S HEL XL 一 9 7 in t h e win GX p a ck a g e 2 J H a t o ms w e r e p la ce d in e al e u la t e d p o s i t i o n s w it h C H d i s t a n ce s o f 0 0 9 3 0 0 9 6 n m a n d N H 0 0 8 6 n m a n d r e fi n e d u s in g a r id in g mo d e l w it h U i H 1 2 1 5 C T h e O R T E P 3 2 d r a win g o f t h e mo le cu le s is s h o wn in F ig 1 a n d F ig 2 C rys t a l a n d e x p e r ime n t a l d a t a a r e lis t e d in T a b le 1 s e le ct e d b o n d le n g t h s a n d a n g le s a r e g iv e n in T a b le 2 Hy d r o g e n b o n d i n g g e o me t ry is g iv e n in T a b le 3 C C DC 9 6 9 6 9 9 L 9 6 9 7 0 0 1 2 Re s u lt s a n d d is cu s s io n 2 1 Cr y s t a l s t r uct ur e o f l iga nd a nd Ag C 8 I I 2 o S 4 NO3 1 T h e crys t a l s t ruct u r e o f t h e lig a n d is s h o wn in F ig 1 T h e lig a n d crys t a lliz e d in t h e o r t h o r h o mb ic d a ta f o rlig a n d L a n d 1 f 0 I L l 翰 0 0 6 0 9 f 0 1 6 1 6 1 P F 2 2 F 2 I 3 f o r 1 1 踊 0 0 4 1 9 尸 0 o o o o e 2 昭 3 2 4 3 6 无机化学学报 第 3 0卷 Ta b l e 2 S e l e ct e d b o n d l e n g t h s n m a n d b o n d a n g le s f o r co mp l e x 1 C1 Cl C1 C2 C2 一 C3 C3 一 N1 C 3一 C3 C1 C1 C2 C3 C2 C l N卜 3 C2 NI C3 C3 C2 一 C3 一 C3 O 1 5 1 5 2 5 2 4 6 5 2 7 4 5 3 3 2 4 2 7 3 1 0 2 5 1 1 9 6f 0 9 1 8 f 0 8 9 5 f l0 7l r C4 Nl C4 C5 C5 一 6 C5 一 C9 N C 4 C5 C6 C5 C 9 C 6 C5 C 4 C9 C5 一 C4 C8 C6 C5 2 5 4 6 3 7 0 1 3 8 9 2 8 2 8 2 1 2 2 2 l 8 f l6 7 0 f 2 2 1 9 f 21 0 8 r l9 4 4 f 5 6 5 6 6 C6 一 C8 C7 N2 C7 C8 N2 C9 N2 C7 C8 C7 一 N2 一 C 9 C4 N1 C3 C7 C8 C6 N2 C9 一 C5 0 1 3 7 3 2 0 1 3 2 1 3 0 1 3 6 2 3 0 1 3 3 7 2 2 3 9 8 f 1 6 2 0 1 8 5 7 r 1 8 8 9 r 2 4 7 8 8 6 4 8 8 N1 一 Ag1 Ol Agl 0 2 3 1 0 3 N2 A g l 0 2 2 8 9 3 N 4 一 A g l 0 2 4 9 6 4 0 2 5 2 0 4 N 2 一 A g l N1 1 4 0 9 2 1 3 N 2 一 A g l N 4 9 2 8 4 1 2 NI A g O1 9 0 3 2 1 2 1 NI A g l N 4 9 2 4 2 1 3 N2 一 A g l Ol 1 2 6 0 4 1 3 N 4 一 A g l O1 1 0 2 4 0 1 2 S y mme h T r e la t io n s 一1 1 2 x 1 2 y x s y s t e m s pa e e g r o u p Pb cn r h e r ma l e llip s o id a l 3 0 le v e l F ig 1 Mo le cu la l s t r u ct u r e o f lig a n d wit h a t o m n u mb e r in g Th e cr y s t a l s t r uct u r e o f t h e co mple x i s s h o wn i n F ig 2 Sin g le cr y s t a l X r a y d if f r a ct io n a n a ly s is r e v e a le d t h a t co mp o u n d 1 cr y s t a lliz e d in t he mo n o cli ni c s p a ce g r o u p C2 Th e a s y mme t r ic u n it o f t h e t i t le co mp le x A g C i s H 2 o N 4 N 0 3 1 w a s co mp o s e d o f t w o A g I J e n t e r s t wo u n i q u e L lig a n d s a n d t w o co o r d in a t e d n it r a t e a n i o n s F ig 3 E a ch s i lv e r i o n h a d a d is t o r t e d t e t r a h e d r a l co o r di na t io n e n v i r o n me n t b e in g bo un d t o t h r e e n it r o g e n d o n o r s f r o m t h e t h r e e a d j a ce n t mo le cu le s f L a n d o n e o x y g e n a t o m fro m n it r a t e a n io n t h e n it r a t e li g a n d s we r e mo n o d e nt a t e Th e Agl N 1 A g l N 2 a n d A g l N 4 b o n d le n g t h s w e r e 0 2 3 1 0 3 0 2 2 8 9 3 a n d 0 2 4 9 6 4 n m a n d t h e A g l O1 b o n d le n g t h w a s 0 2 5 2 0 4 1 n m T h e N A g N a n g le s w e r e in t h e r a n g e 8 4 1 2 1 4 0 9 2 1 3 a n d t h e 0 A g N a n g le s r a n g e d fr o m 9 0 3 2 1 2 t o 1 2 6 0 4 1 3 I n co m p o u n d 1 t h e L li g a n d s co o r d in a t e d t o t h e A g I i o n s in t w o d if f e r e n t w a y s F ir s t I w a s b o u n d t o A g I ce n t e r s in 第 1 0期 张奇龙等 v 一 双 3 吡啶醛 一 1 R 2 R 一 环己二胺席夫碱 A 1 配合物的合成 结构和荧光性质研究 2 4 3 7 C 2 F ig 2 T h e r ma l e llip s o id p lo t a t 3 0 le v e l o f t h e a s y mme t r ic u n it s o f t h e co mp le x 1 F i g 3 a C o mp le x o f A g I i o n co o r d i n a t io n mo d e s b L i g a n d s w it h d i f f e r e n t co o r d i n a t i o n p a t t e r n s a b r id g in g b i d e n t a t e mo d e t h r o u g h t h e t e r min a l p y r i d y l N d o n o r s o n ly He r e t h e in n e r imin o N a t o ms w e r e o r ie n t e d in d i f f e r e n t d ir e ct io n s w it h n e a r ly g a u ch e N C C N t o r s io n a n g le s e q u a l t o 6 4 8 4 Th e d is t a n ce b e t w e e n t h e t w o A g I ce n t e r s w a s 1 1 0 6 4 n m T h e s e co n d b i n d in g mo d e f o r L wa s co o r d in a t io n t o A g I i o n s in a t e t r a d e n t a t e f a s h io n t h r o u g h b o t h t e r min a l p y r id y l N d o n o r s a n d b o t h in n e r imin o N a t o ms Th e la t t e r we r e o r ie n t e d in di ffe r e n t d ir e ct io ns wit h t he n e a r ly g a u ch e N C C N t o r s io n a ng le s e q u a l t o 5 9 6 9 Th e d is t a n ce t h a t t h e t wo ni t r o g e n a t o ms o n t h e p y r id in e r in g co o r d in a t e d A g I io n s w a s 1 1 9 7 9 n m T h e ch ir a l lig a n d s r e s u lt e d in a co o r d i n a t io n co n f i g u r a t i o n in wh ich a b id e n t a t e p y r id y l n it r o g e n a t o m w a s co o r d in a t e d t o Ag I wh i ch in t u r n w a s co o r din a t e d t o a t e t r a d e n t a t e p y r id y l nit r o g e n Alt e r n a t io n o f t h is s e qu e n ce u lt ima t e ly g e n e r a t e d t h e 1 D ch a in s t r u ct u r e h e lix F ig 4 o b s e r v e d cr y s t a l lo g r a p h i ca lly Fu r t he r mo r e imin o n it r o g e n a t o ms in t h e t e t r a d e n t a t e li g a n d s w h i ch w e r e lo ca t e d o n t h e o pp o s it e s id e s o f t h e li g a n d b r id g e d he lix co o r d in a t e d d if f e r e n t Ag I i o n s in o t h e r h e lice s s u ch t h a t t h e s u p r a mo le cu la r a s s e mb ly o f co mp le x 1 w it h b o n d s co n n e ct e d t hr o u g h a 3 D p o r o us n e t wo r k s t r u ct ur e wa s F ig 4 I D r ig h t h a n d e d h e lica l ch a in in t h e co mp le x 1 F ig 5 P a r 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