Nghiên cứu điều chế một số ligand họ pyridinium làm tiền chất để tổng hợp MOFs



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





s












 CHÍ MINH, 12/2011
 i





   
Tp.HCM, ngày 19 tháng 12 


:  Phái: Nam
Ngày sinh: 24-11-1983  
Chuyên ngành:  MSHV: 09050122
Khoá: 2009
1. 

N:
- t s hp cht carboxylate có cha nhóm pyridinium làm
cu n tng hp vt li-kim (MOFs) mi.
- 
.
1-05-2011.
4. 01-12-2011.
5.  CBHD1: T
CBHD2: PGS.TS. 
ôn.





LÝ CHUYÊN NGÀNH

KHOA QL CHUYÊN
NGÀNH


 ii









: CBHD1: 
CBHD2: PGS.





 


 




11

 iii






:
 

.
 . Lê 


2011).



.





-.







 iv







ABSTRACT

A series of five unprecedented flexible zwitterionic ligands 1-5 which are
pyridinium carboxylate ligands has been developed. These ligands were designed to
be different in the flexibility and size for subsequent application as linkers in the
construction of new metal-organic frameworks (MOFs) and study their influence on
the structural topologies of the architectures obtained. All three ligands were fully
characterized by 1H, 13C NMR, mass and IR spectroscopies.

 v




Trang
 .................................................................................................
 ................................................................................................... iii
ABSTACT ........................................................................................................... iv
 ........................................................................................................... v
 ........................................................................................... ix
 ............................................................................... xii
........................................................................................xiii
 ................................................... xiv
 ..................................................................................................... 1


.................................................................................................................... 2
 mofs)
 ..................................................................................... 2
1.1.2 .................................................................... 5
 ......................................................................... 5
............................................................................. 5

 ................................................................... 6
 ......................................................... 6
 ......................................................................................... 7
 ............................................................................... 8
1.1.3.4.  ..................................................................... 8
 ............................................................................... 9
 ......................................................... 12
 ........................................................... 12
 ....................................................................... 13
 ...................................................................... 13
 vi



 ........................................................................... 14
1.1.5.1.. Xúc tác ......................................................................................... 16
 ................................................................................... 17
 ...................................................................................... 23
 .................................................................................... 28
 ............................................. 29
 ...................................................................... 32
 ......................................................................... 33
p MOFs ............. 34
................................................. 34
 ................................... 38
 ............................................................................ 41
 ................................................................. 41
 .............................................................................. 41
 ............................................................................... 41
 ........................................................................ 41

 ........................................................................ 41
2.1.3.2 ...................................................................... 43
 ....................................... 44
d-1 (4,4'-(ethane-1,2-diyl)bis(1-(4-
(carboxymethyl)benzyl)pyridinium) bromide) ..................................................... 44
d-2 (4,4'-disulfanediylbis(1-(4-carboxybenzyl) pyridinium)
bromide) ............................................................................................................. 46
-3 (1,1'-(1,4-phenylenebis(methylene))
bis(4-(carboxymethylthio)pyridinium) bromide ............................................. 48
-4 (1,1'-(5-((3-(carboxymethylthio)pyridinium-1-
yl)methyl)-1,3-phenylene)bis(methylene)bis(4-(carboxymethylthio)pyridinium)
bromide) .............................................................................................................. 50
 vii



-5 (1,1'-bis(4-carboxybutyl)-4,4'-bipyridine-1,1'-diium
bromide) .............................................................................................................. 52
 .......................................................... 54
-1 .................................. 54
-1 ............................................................................ 54
-1 ................................................. 54
-2 .................................... 60
-2 (4,4'-disulfanediylbis(1-(4-carboxybenzyl)
pyridinium) bromide) .......................................................................................... 60
and-2 ................................................. 60
-2 .................................. 60
-3 (1,1'-(1,4-phenylenebis(methylene))bis (4-
(carboxymethylthio)pyridinium) bromide)........................................................... 66
-3 ................................................ 67

3.4. -4
-4 ............................................................................. 73
-4 ................................................. 74
-5 .. 78
-5 ............................................................................. 78
-5 ................................................. 78
 ........................................................ 83
 .............................................................................. 83
 ............................................................................................... 84
 .................................................. 85
 ................................................................................. 86
 .......................................................................... 89
1 ............................................................................................................. 90
2 ............................................................................................................. 93
3 ............................................................................................................. 96
 viii



4 ............................................................................................................. 99
5 ........................................................................................................... 102
 ix




Hình 1.1. Cu trúc không gian ca các vt liu MOFs ..................................... 3
1.2.-5 .............................................................................. 4
1.3.-5 ............................................................. 5
1.4.-31, MOF-32, MOF-33 ......................... 7

Hình 1.5. Thit k và tng hp cu trúc hóa hc có din tích b mt cao ......... 8
1.6.  ..................................................... 9
1.7. ............................................................................. 9
1.8.  ........................................................ 11
1.9.  ......................................................... 15
1.10.  .................................... 16
1.11. -53 có nhóm µ
2
-OH là trung tâm acid ............... 17
 1.12.  ......................... 18
1.13.  ....................... 19
1.14.-3 .......................................................... 19
1.15.       
 .............................................................. 20
 1.16. -  ................ 20
1.17. --

o
K .............................................................................................. 21
1.18.Cu
2
(pzdc)
2
(pyz), C
2
H
2
(màu vàng) ti 170
o
ng

ng nhit hp ph ti 300
o
K ........................................................................... 22
1.19. Cu(fma)(4,4

-bpe)
0.5
.

................................... 23
1.20. S hp ph khí ca Cu(dhbc)
2
(4,4

-bpy). ..................................... 24
1.21. ng hp I ph ng nhit H
2
trên các MOFs khác nhau ..... 25
1.22. Cu trúc MOF-177 ...................................................................... 25
1.23. ng nhit H
2
trên các IRMOF và MOF-177 ti 77
o
K ..... 26
1.24. Kh  CO2 ca MOF-177 ........................................... 27
1.25. So sánh kh p ph CO
2
trên các MOFs khác nhau .......... 27
 x



1.26. Tính bn nhit và kh p ph Methane ca IRMOF-6 ....... 28
1.27. Kh p th khí metan ca mt s MOFs tiêu biu.............. 29
1.28. -EMOF
[28]
............................ 30
1.29.  ... 32
1.30.  
mmol NO/g MOF. ............................................................................................ 32
1.31. -CPO- ....... 33
1.32.   .................................................. 34
1.33. Pyridinium ................................................................................... 39
1.34. Ligand 1,4-Diazoniabicyclo[2.2.2]octane-l,4-diacetate ................ 41
2.1.-1 ...................................... 45
Hình 2.2.-
 .................................................................................................................. 46
2.3.-2 ..................................... 47
Hình 2.4.-
 .................................................................................................................. 48
2.5.-3 ...................................... 49
2.6.-3 qua 3 h ...... 50
2.7.-4 ..................................... 51
2.8.-4 qua 3 h ...... 52
2.9. -5 ............................................... 53
Hình 2.10.-
 .................................................................................................................. 54
3.1.-1 ..................................................... 55
3.2.-
-

1
H....................................................................................... 57
3.3.
1
-1 ............................................................. 57
3.4.
13
-1 ............................................................. 59
3.5.--1 .................................................................. 60
 xi



3.6.-1 .................................................................... 61
3.7.-2 .................................................... 61
3.8. -
-
1
H ............................................................................................. 63
3.9.
1
-2 ............................................................. 63
3.10.-
13
-2 .......................................................... 66
3.11.--2 ............................................................... 67
3.12.-2 ........................................ 68
3.13.-3 ................................................... 68
3.14-
 NMR-

1
H .................................................................................................... 70
3.15.
1
-3 ........................................................... 70
3.16.
13
-3 .......................................................... 73
3.17.--3 ............................................................... 74
3.18.-3 ........................................ 76
3.19.-4 ................................................... 77
 3.20.   P.  -       trên 
NMR-1H .......................................................................................................... 78
3.21.
1
-4 ........................................................... 78
3.22.--4 ............................................................... 80
3.23. -4 ........................................................ 81
h 3.24. -5 ................................................... 82
3.25.-
-
1
H .................................................................................................... 83
3.26.-
1
gand -5 .......................................................... 84
3.27.--5 ................................................................ 85
3.28.-5 ........................................................ 86

 xii




1.1.  ................................................................................ 9
1.2. hình hc, thành phn và liên kt ca SBU ...................... 11
1.3. Tính cht ca các loi IRMOFs và kh p ph Methan........................27
Bng 1.4. Các phân t hc s d to liên kt ht ni
các tâm kim loi vi nhau trong quá trình tng hp vt liu MOFs ........................38
2.1. ................................... 42
ng 2.2.d ................................. 43
3.1. (-
1
H
-1 .......................................................................................................... 55
3.2. dch chuyn hóa h NMR-
13
C
caligand-1 .......................................................................................................... 57
3.3. Các t
-1
-1 ................................. 58
3.4. (-
1

ligand-2 ............................................................................................................... 61
3.5. dch chuyn hóa h NMR-
13
C ca

ligand-2 ............................................................................................................... 63
3.6. 
-1
-2 ................................ 65
3.7. (-
1

ligand-3 ............................................................................................................... 67
3.8. dch chuyn hóa h NMR-
13
C ca
ligand-3 ............................................................................................................... 69
3.8. 
-1
) -3 ................................ 71
3.9. (-
1

ligand-4 ............................................................................................................... 74
3.10. 
-1
-4 ............................... 76
3.11. (-
1

ligand-5 ............................................................................................................... 79
3.12. 
-1
 ligand-5 .............................. 80
 xiii





1.1. -ethynylaniline, amine, aldehyde, xúc tác
IRMOF-3-SI-Au trong dioxane ..................................................................... 16
 1.2.  tng hp 1,3-azulenedicarboxylic acid ............................... 35
 1.3.  tng hp N, , -trimethyl-N, , -tris(3-pyridyl)-1,3,5-
benzenetricarboxamide .................................................................................. 35
1.3.1,3-bis(pyridinio-4-carboxylato)-propane .......... 35
1.4.1,3-bis(pyridinio-4-carboxylato)-propane .......... 39
1.5.1,3-bis(pyridinio-4-acetato)-propane .................. 39
1.6. T1,4-Bis(pyridinio-4-carboxylato)-1,4-dimethylbenzen....39

 xiv





BDC 1,4-benzenedicarboxylates
d Doublet
DEF N, N-Diethylformamide
DMF N, N-Dimethylformamide
DMSO Dimethyl sulfoxide
EtOH Ethanol
Et
2
O Diethyl ether
EtOAC Ethyl Acetate
FT-IR Fourier Transform Infrared
HCl Hydrochloric acid
IRMOFs Isoreticular Metal Organic Frameworks
KOH Potassium Hydroxide
MeOH Methanol
MOFs Metal Organic Frameworks
MP Melt point
MS Mass Spectrometry
NMR Nuclear Magnetic Resonance Spectroscopy
s Singlet
SBUs Secondary Building Units
THF Tetrahydrofuran
TLC Thin layer chromatography

 Chemical shift




 1




ng hong
v ngun nhiên li. Bên cc
t cháy nhiên liu phc v cho nhu cu sn xui si vào bu khí
quyn mng ln các khí gây hiu  nht là CO
2


               
               



(MOF).

ligand - u ni ht trong hai thành phn chính to nên
vt li-



t.

              
 
 
-kim (- 
.
 2






PYRIDINIUMOFs
 
1.1.1. Lch s phát trin

u và s dng nhng loi
vt liu có cu trúc x
hp ph... Tuy nhiên, nhng vt liu này có cu trúc mng l xp không
. Vì vy các nhà khoa h gng nghiên
cu ra nhng cu trúc x.


-
MOFs
[1]
.

            
Cu(NO3)

2
-1,3,5-Trazine
[2]
.

          -    
Hydrogen
[3]
.

      
  
                

 

 3



, 
khí H
2
-1, IRMOF-8, IRMOF-18, IRMOF-11 và MOF-177.

Hình 1.1. Cu trúc không gian ca các vt liu MOFs vi các liên kt h
 carboxylic acid kt ni các tâm kim loi vi nhau, do nhóm nghiên cu ca
GS Omar M. Yaghi tng hp ra. Hình cu trúc minh ha cho không
gian ln nht có trong l xp mà không b ng c
Waals vi khung h kim loi

[4]
-69A  C, MOF-70 

      -   
(Fe
3
O)
4
(SO
4
).12(BPDC)
6
(BPE)
6
. 

2
-
Zn
4
O(COO)
6
-benzenetribenzoic acid, c
ng

[5]
.
Nhóm nghiên cu c i thành phn ca các
nhóm kim loi - hm to ra nhng cu trúc vt liu m
t trng vt li bn nhit, din tích b

mt riêng ln, cu trúc l xp vng chng nhiu ng dng rng rãi,
 4



y ha hn ca nhng loi vt liu x xúc tác, phân
tách hn h 


1.2.-5
[6]

(MOFs) là nhóm vt liu lai m
da trên s liên
kt ca các ion ca kim loi chuyn tip và các cu ni h



[7]
.
MOFs gm nhng nhóm cation kim loi vi các nhóm carboxylate, mt cu
nc dùng làm tác nhân phn ng hình thành mt khi t din vi
mnh là mt nhóm carboxylate kim loi. Tính cht ca các cu ni h
nhau là khác nhau và là nht bin, chúng cho phép quá trình lp ghép các cu ni
vào b khung không gian ba chiu ca vt liu MOFs là duy nht, cu trúc vng
chc này có din tích b mt riêng ln và th tích mao quu ht các loi
cu trúc xp khác. MOFs là mt ti   nh
ng nghiên cu vt liu composite mi
[8]
.

 5




[1]
Vt liu MOFs gm nhng tâm ion kim loi liên kt vi các cu ni h
to nên b khung h- kim loi vng chng giàn giáo xây dng, bên
trong b khung là nhng l trng to nên mt h thng xp vi nh
ch là nhng phân t.
1.1.2.1. 
Các tâm ion kim loi tng là các cation Zn
2+
, Cu
2+
, Co
2+
, Pb
2+
i
kim lo    tng hp là loi ng   
3
)
2
.6H
2
O,
Co(NO
3
).6H

2
O, Cu(NO
3
).4H
2
O, Co(CH
3
COO)
2
.4H
2


1.3.-5
1.1.2.2. 
Các phân t hu c dng trong quá trình tng hp MOFs s to ra các liên
kt hi tâm kim loi.
Các phân t hng là diacid ha hai nhóm  COOH. Ngoài
ra còn có các nhóm ch       
cha các nhóm chc s dng làm cu ni.
Vic la ch c tng hp nên vt liu MOFs phc
la chn mt cách cn th các tính cht c cu trúc này phc
bo toàn và sn phm MOFs phc nhng tính chi các vt liu
copolymer hn cht và n ca các monomer trong polymer
 6



quyc tính vc tính quang h  gia
công hay x i vi vt liu MOFs, cách b trí mi liên k

v cu trúc trong sn phm MOFs li quynh ch yu lên tính cht ca MOFs.
Quá trình tng hp vt liu MOFs không ch yêu cu vic la chu ch ra
các module mong mun, mà còn yêu cu phi d c chính xác cách
sp xp các module này trong sn phm vt liu dng rn sau cùng
[9]
.

1.1.3.1. 
Vô t các cu trúc ca MOFs là mt v ó có 
hp lý m phân loi nó m. Nhóm nghiên cu ca
  cùng cng s n khái nim SBUs. Da vào  xây
dng th cp (SBUs) mà có th c cu trúc hình hc ca các vt liu
tng hp, t t k và tng hp các loi vt liu xp mi có cu trúc và trng
thái xp cao. Pha MOFsc g xây dng (SBU), có
th c mô t bi các cu trúc liên kt chung cho mt s cu trúc. Mi cu trúc
liên kc gi là mt mc ch nh mt biu tng, gm ba ch
m. 
.

1.4.-31, MOF-32, MOF-33
[10]
 7



 xp cao



. 

[11]
.
Tng hp vt liu có din tích b mt (DTBM) ln là mt v thách thc
ln ca các nhà nghiên cu. DTBM cao nht ca cu trúc mt trt t carbon là 2030
m
2
/g, cu trúc trt t zeolite Y là 904 m
2
c bit vi khung h kim loi,
din tích b mt lên ti 3000 m
2
/g, MOF-t 4500 m
2
/g
[12]
, MOF-t 8000
m
2
/g.

c hin ct mng ln thành mnh nh 
DTBM theo hình 1.3, DTBM mnh l
2
/g hình 1.3a, chui các vòng
sáu liên kt  v m
2
/g hình 1.3b, chia mnh graphene ln
 3 vòng liên kt vi vòng trung tâm  v trí 1,3,5-t 6200
m
2

/g hình 1.3ct 7745 m
2
/g hình 1.3d. T kt qu phân tích này tác gi
nhnh tránh cc s a s t, các cnh.


Hình 1.5. Thit k và tng hp cu trúc hóa hc có din tích b mt cao
[13]
 8



1.1.3.3. Ví trí kim loi m
i vi mt s, lc liên kt gia các chùm kim loi và dung môi
rt yu chúng d c loi gia nhit, khi dung môi b lo
h- kim và s xut hin v trí kim loi mi vi
nhng phi t  v trí trc liên kt vi kim loi theo s bin dng Jahn-Teller, d
thy nht là các ion Cu
2+
ng phi t làm cho s liên kt ca phi t trc yu,
kt qu phân t dung môi ri khi tâm kim loi
[13]
.

1.6. 
a) SBU Cu II carboxylate - 
2

c) MOF-
1.1.3.4. Mi ging zeolites

[11]

1.7. 
 9



--40, các rãnh elip
-
CTC trong JUC- -

Mt s cch anh, rutil (SiO
2
), PtS và khoáng
ch c ch to gi bng cách thay th  (O
2-
, S
2-
)
bng cu ni hkim lo
phá Cd(CTC)(H
2
O).(H
2
PIP)
0.5
(H
2
O)(JUC-40) có dng zeolite aluminosilicate,
Dollase và Ross phát hin Cd(CTC).(HIPA)(JUC-41) có dng zeolite tectosilicate

t din.
1.1.3.5. Cu trúc mnh
Nhìn chung, mt s ci xng cao, da vào hình
dng ca chúng mt s cc mnh theo bng 1.1 và mi theo
hình 1.8
[12]
.
1.1. 
S phi trí Tên Mng Hình Transitivity
3 SrSi
2
Srs Tam giác 1111
4 NbO Nbo Hình vuông 1111
4  Dia T din 1111
6 L Pcu Bát din 1111
8 Body-centred
cubic
Bcu L 1111
12 Face-centred Fcu Cuboctahedron 1112
 10



cubic
6 Acs  tam giác 1122
4,8 Fluorite (CaF
2
) Flu T din, l 2111
3,6 Pyrite (FeS
2

) Pyr Tam giác, t din 2112
3,4 Pt
3
O
4
Pto Tam giác, hình
vuông
2122
3,4 Boracite Bor Tam giác, t din 2122
4,4 PtS Pts Hình vuông, t din 2122
6,6 NiAs Nia , bát din 2122
Có p lonh, q loi cnh, r loi mt, s loc tính transitivity là
dãy sp xp các s nguyên pqrs, nu có nhi  t lo   i xng.
 i. Vì th, cu có
transitivity là 1111, k 

1.8. 