TAP CHI HOA HOC T. 51(6) 672-676 THANG 12 NAM 2013
T 6 N G HCyP VA NGHIEN CLKU PHU'C C H A T
NAPHTHOYLTRIFLOAXETONAT CUA MOT SO NGUYEN TO DAT HIEM
Trieu Thi Nguyet^*, Dinh Thi Hien^ Nguyin Minh Hdi', Nguyen Hiing Huy', Cao Thi Ly' 'Khoa Hoa hoc, Trudng Dgi hgc Khoa hgc Tu nhien. Dgt hoc Quoc gia Hd Ngi
'Khoa Hoa hoc, Tnrdng Dgi hgc Supham Hd Npi D^n Toa soan 19-3-2013
Abstract
The naphthoyltnfluoroacetone of Y, Pr, Nd, Sm, Eu, Tb, Ho, Er has been prepared. The complexes were characterized by IR, elemental analysis and NMR. The 'H-XNIR. '""C-NMR, IR result showed that the coordination mode IS through the oxygen atoms of the diketone group.
Keyvvords: Rare earth, p-dixetone, luminescent materials, complexes.
1. MO DAU
Cac P-dixeton dugc ung dung trong nhieu ITnh vuc khac nhau. Chimg dugc su dung de xac dmh cac ion kim loai trong dung djch loang bang phuang phap trac quang va trong phan tach sac ki. Mot so |3- dixetonat dat hiem ddng vai trd quan trgng la tac nhan dich chuyen trong phd cdng hudng tir, trong y hgc [1] Mpt sd P-dixetonal dat hiem da dugc iing dung de che lao didt phat quang cho cac loai man hinh phang da mau vdi gia thanh thap [2-4]. Tuy nhien, van chua cd cdng trinh nao tdng hop va nghien ciru cac P-dixeton cd cau tnic dai phan tir va polime phoi tri, cung nhu phiic chat ciia chimg vdi cac nguyen to dat hiem. Vi vay chiing toi tien hanh tdng hop va nghien cuu tinh chat phuc chat naphthoyltnfloaxetonat ciia Y, Pr, Nd, Sm, Eu, Tb, Ho, Er.
2, THUC NGHIEM
Chiing tdi chua tim thiy tai lieu nao noi ve qui trinh tdng hgp cac phiic chat naphlhoyltrifloaxetonat cua Y, Pr, Nd, Sm, Eu, Tb, Ho, Er. Viec tdng hgp cac phirc chat nay dugc md phdng theo qui trinh tong hgp phirc chat 2-(2,2,2-trifloelhyl)-l-indonat ciia Eu, Sm trong tai lieu [1].
2.1. Tdng hffp cac naphthoyltrifloacetonat dat hiem
Hon hgp gdm 0,6 mmol natrihidroxit va 0,6 mmol naphthoyitrifloaxeton (TNB) trong 30 ml
etanol duo'c khuay deu trong 15 phut. Them tir tir 0,2 mmol LnCl3 6H2O vao hdn hgp tren, khuay deu trong 24 gid d nhiet do phdng. Sau dd, them khoang 10 ml CCI4 vao hdn hgp, phirc chat dugc tach ra.
Lgc, rua ket tiia bang CCI4 va lam khd d nhiet do phong. Mau sac ciia cac san pham dugc md ta trong bang 1. Hieu suit 70-80%.
2.2. Cac phuong phap nghien ciru
Ham lugng ion dat hiem trong cac phuc chat duac xac dinh bang phuang phap chuan do complexon dua tren phan irng tao phiic ben ciia ion dat hiem vdi EDTA d pH = 5 va chat chi thi la asenazo III.
Phd hdng ngoai dugc ghi tren may FTIR 8700, trong vimg 400-4000 cm"', theo phuong phap ep vien KBr lai Vien Hda hgc, Vien Han lam Khoa hgc va Cdng nghe Viet Nam
Phd cong hudng tir hat nhan 'H-NMR va ''C- NMR ciia Y(TNB)3(H20)2 dugc ghi tren may Bruker-500MHz d 300 K, dung mdi CD3OD tai Vien Hda hgc, Vien Han lam Khoa hpc va Cdng nghe Viet Nam.
3. KET QUA VA THAO LUAN
3.1. Ket qua phan tich ham luong kim loai trong phiic chat
Ket qua d bang 1 cho thiy, ham lugng kim loai tinh iheo cdng thiirc gia djnh cua cac phirc chit tuang ddi phii hgp vdi ket qua xac dinh bang thuc nghi?m.
TCHH, T. 51(6), 2013 Trieu Thi Nguyet vd cgng su 3.2. Pho hdng ngoai ciia cac phirc chat dua tren viec so sanh phd cua
Viec qu> kk dai hip thu trong phd hong ngoai chiing vdi pho ciia phoi hi tu do (bang 2).
Bdng J. Ket qua phan tich ham lugng kim loai trong cac phiic chit
S T T
1 2 3 4 5 6 7 8
Cong thirc gia dinh cua phirc chat
Y ( T N B ) , ( H , 0 ) 2 Pr(TNB)3(H20)2 N d ( T N B ) 3 ( H , 0 ) , Sm(TT,lB)j(H,0), Eu(TNB)3(H20)2 T b ( T N B ) j ( H 2 0 ) , Ho(TNB)3(H20)2 E r ( T N B ) j ( H 2 0 ) i
M a u sac cua phu:c chat
T r a n g X a n h Tiin nhat V a n g nhat V a n g nhat V a n g nhat Hong nhat H o n g
Ham l u g n g ion kim loai trong p h u c chat, % Ly thuyet
9,67 14,50 14,77 15,29 15,46 16,06 16,57 16,73
Thirc nghiem 9,62 14,46 14,75 15,21 15,42 16,02 16,54 16,70
Bang 2: C a c dai hap thu dac t m n g trong pho hong ngoai cua phirc chal va phoi t u (v. c m ' ) STT
1 2 3 4 5 6 6 8 9
H g p chat TTffi Y(TNB),(H20)2 Pr(TNB)3(H20)2 Nd(TNB)3(H20)2 Siti(TNB)j(H20)2 Eu(TNB)3(H20)2 Tb(TNB)3(H20)2 Ho(TNB)j(H20)2 Er(TNB)3(H20)2
V,0-H 3459 3421 3418 3430 3 4 1 0 3412 3407 3449 3 4 3 4
VsCll 3067 3065 3062 3060 3109 3058 3072 3074 3063
VsC-O 1601 1615 1608 1613 1613 1614 1609 1612 1609
V,C-F 1191 1301 1289 1289 1298 1296 1294 1299 1301
V, M-O
577 572 574 619 570 574 570 575
Hmh I: Phd hdng ngoai cua TNB
Tren pho hdng ngoai cua phoi tir, dai d vimg cd so sdng 3459 cm"' dac trung cho dao ddng hda trj cua nhdm OH ciia phdi tii dang enol (hinh 1). Tren phd cua cac phiic chit, cac dai hap thu tii va rgng cd cudng dp trung binh trong vimg 3407-3449 cm"
dugc qui gan cho dao dpng hda trj cua nhdm -OH h-ong phan tir HiO phoi tri. Cac dai trong vung 3060- 3109 cm"' thugc ve dao dpng hda tri ciia nhdm =CH ciia vdng therm napthalen. Dai hap thu tai 1601 cm'
Hmh 2: Phd hdng ngoai cua Eu(TNB)3(H20)2
dac trung cho dao dgng ciia nhdm C=0 trong phdi tir dich chuyen ve viing cd sd sdng cao han trong cac phiic chat (1608^1615 cm"'). Chiing tdi cho ring su dich chuyen nay la do anh hudng cua hi^u irng lien hgp ciia vdng dixeton va cua nhdm naphtalen. Ciing do hieu irng nay ma dai hap thu C-F ciia phdl tir d 1191 cm"' da djch chuyen ve viing ed sd sdng cao ban trong cac phirc chat (1289-1301 cm ') So vol phd hap thu hong ngoai ciia phdi tir. trong phd ciia
TCHH, T. 51(6), 2013
tit ca cac phiic chat xuat hien them cac dai hap thu dac trung vdi cudng dp trung binh trong vitng 570-^619 cm"', dugc quy ket cho dao ddng hda trj ciia lien ket M-O (hinh 2). Cac ket qua nay cho thay da cd su hinh thanh lien ket giira cation kim loai va phdi tu qua nguyen tir O.
3.3. Cong hudng tir hat nhan
De xac dinh chinh xac hon cau true ciia phtic chat, chimg tdi chpn mdt phirc chat dai dien la phirc chat Y(lll) de nghien ciiu bang phuong phap phd cdng hudng tu hat nhan 'H va '^C.
Hinh 3 la phd cdng hudng tir hat nhan 'H ciia phirc Y(TNB)3(H20)2, su qui gan cac tin hieu dugc trinh bay d bang 3. Sd tbii lu cac H ciia naphtalen duac chi ra trong hinh 6.
Tong hap vd nghien ci'mphuc chdl..
Bdng 3: Sir qui gan cac tin hieu tren pho'H-NMR ciia Y(TNB)3(H20)2
STT 1 2 3 4 5 6 7 8
Vi tri, ppm 8,54 8,05 7,86 7,81 7,65 7,54 7,40 6,67
Dac diem singlet doublet doublet doublet doublet triplet triplet smglet
Tich phan 2,0 2,0 2,0 2,0 2,0 2,0 2,0 2,0
Qui gan IH ciiaC, IH cuaC3 IH cuaC, IH ciiaCj IH cCiaC, IH cuaC, IH ciiaC, IH cua nhom
C-H
My \ i ; / VM/ \i,''
J'l/
Hmh 3 Pho'H-NMR ciia Y(TNB)j(H,0)2
il li
I,
iii!* m
Hiiili 4: Ph6 'H-NMR ciia ph6i lir TNB
674
TCHH, T. 51(6), 2013 Trieu Thi Nguyet vd cgng su Bdng 4: Cac tin hieu tren phd ' H - N M R ciia TNB
STT 1 2 3 4 5
Vj tri, ppm 8,61 8,58 8,05-7,91 7,67-7,57
Tich phan 1,0 4,0 2,0
Dac diem 2 multnplet 2 multnplet 2 multriplel
Qui gan H,-naphtalen ciia dang xelon
H|-naphtalen ciia dang enol Cac H con lai ciia naphtalen Khong quan sat dugc tin hieu proton ciia -CH, ciia dang xeton
hoac-CH va-0-H...O-cua dang enol Tren pho cdng hudng tir hat nhan H ciia Y(TNB)3(H20)2, tin hieu singlet d 6,67 ppm vdi ti le tich phan 2 dac trung cho proton cua dixeton dugc qui gan cho IH cua nhdm CH. Cac tin hieu d 8,54-^7,40 ppm vdi ti le tich phan la xap xi 2:2:2:2:2:2 2 dac trung cho proton cua vdng thom, chiing tdi qui gan cho 7H ciia vdng naphtalen. Viec qui gan chii yeu dua tren su phan tach ciia cac tin hieu va ti !e tich phan thu dugc. Tin hieu ciia proton irng vdi cac H cua nudc trong phuc chat khdng quan sat dugc cd the do chiing triing vdi tin hieu proton ciia nudc cd trong dung mdi d 4,88 ppm. Viec so sanh phd cdng hudng tir hat nhan 'H ciia phdi tu TNB (hinh 4, bang 4) vdi phd 'H ciia phuc chat Y(TNB)3(H20)7, cho phep kel luan da co su tao phiic giua Y(lll) vaphdi tir.
Tren phd ' H - N M R cua TNB khdng quan sat dugc tin hieu proton cua -CH2 (dang xeton) hoae -CH va -0H...0- (dang enol) do su chuyen dichgiua hai dang xeton va enol xay ra nhanh.
De khang dinh them ve cau triic ciia Y(TNB)3(H20)2, chiing tdi sii dung phuang phap cpng hudng tir '^C (hinh 5, bang 5), Tren phd '""C- NMR xuit hien 14 tin hieu cgng hudng irng vdi bp
khung cacbon ciia phan lir Y(TNB)3(H20)2. Hai tin hieu d 189,5 ppm va 172,5 ppm dugc qui gan cho 2 nguyen tir C ciia nhdm C=0. Tin hieu quartet d 120,5 ppm ling vdi C ciia nhom C-F, tin hieu don bpi d 93,3 ppm irng vdi C ciia nhdm CH viing xeton.
Cac tin hieu d 137-125,2 ppm dac trung cho cacbon vong tham dugc qui gan cho 10 cacbon ciia vong tham. Do viec qui gan lung tin hieu la phirc tap va khdng can thiet nen chung tdi khdng qui gan cu the timg tin hieu cho C ciia vdng naphtalen.
Bang 5: Cac tin hieu tren phd ' C-NMR ciia Y(TNB)3(H20)2 STT
1 2 3 4 5
Vi tri, ppm 189,5 172,5 120,7 93,3 137-125,2
Dac diem Singlet Quartet Quartet singlet singlet
Qui gan 2CciiaC=0
C ciia C-F C ciia C-H IOC ciia vong
naphtalen
I I
lullMlH»Uiuk^
,-J.
Hii:h 5 Ph6 "C-NMR ciia Y(rNB),(H20),
675
T C H H . T. 51(6), 2 0 1 3
5 4
Tong hgp vd nghien cuu phuc chdt...
. C F 3
o o
Hmh 6: Phdi t u T N B (a). Phirc chat Ln(TNB)3(H20)2 (b) Tir cac ket qua thu d u g c bang phan tich nguyen
to, p h u o n g phap pho hdng ngoai va p h u o n g phap c p n g h u d n g lir hat nhan, chiing tdi d u a ra gia thiet ve cong thiic cau tao ciia cac phuc chat n h u tren hinh 6.
4. K E T LUAN
Da long hgp d u g c 8 phirc chat bac hai Ln(TNB)3(H20)2 (Ln = Y, Pr, N d . Sm, Eu, T b , Ho, Er), va nghien ciru cac san pham thu d u g c bang p h u a n g phap phd h d n g ngoai. Da nghien cuu phirc chat Y(TNB)_i(H20)2 b a n g p h u a n g phap cdng h u d n g tir hat nhan ' H va '""C. Ket qua cho thay cd su phdi tri giira phdi tir va cac ion kim loai qua cac nguyen tir oxi ciia xeton va trong thanh phan ciia phirc chat cd nudc,
Loi cam o n : Nghien ci'm ndy dirac ldi trg bdi Quy phdt tnen khoa hoc vd cong nghe quoc gia (NAFOSTED) trong c1e tdi. ma s6 104 02-20! 1 31.
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