,a, Ly vd Sinh hgc - Tap 19. So 2/2014
TONG HOP VA NGHIEN CU'U P H f C CHAT HON HOP CUA MOT SO DAT HIEM v O l NAPHTHOYLTRIFLOAXETON VA BIS-PYRIDIN
Din tda sogn 27 - 5 - 2013
Trieu Thi Nguyet, Nguyen Minh Hai, Nguyen Hung Huy Klioa Hda hgc. Tru&ng Dgi hgc Khoa hgc Tu nhien, Dgi hgc Quoc gig Hd Ngi
Dinh Thj Hien
Khoa Hoa hgc, Tru&ng Dgi hoc Su Pham Hd Not
SUMMARY
SYNTHESES AND CHARACTREIZATIONS OF SOME TERNARY RARE EARTH METAL COMPLEXES OF NAPHTHOYL TRIFLUOROACETONE AND
BIS-PYIUDINE
Ternary complexes of rare earth metals Y, Pr, Sm. Eu. Tb. Ho with naphthoyl trlfiuoroacetone and bis-pyridine were prepared. IR and NMR spectroscopies were utilized for structural characterizations ofthe complexes. The results confirmed that the coordinated water molecules were displaced by bis-pyridine and that the coordination of the central metal ion is through oxygen atoms of fl-diketone Hgand and nitrogen atoms of bis-pyridine.
Keyword(s): Ddt hiim; fl-dixeton; vdt lieu phdt quang; phiec chdt.
I . M O D A U thanh thip [2,3,4]. Cac p-dixetonat dit Cac P-drxeton dupc iing dung frong hiem thudng dupc phan lap vdi hai phan nhiSu llnh vuc khac nhau. Chiing dupc sii tii nudc phfli tri vdi nguyen tii trung tam.
dung di xac dinh cac ion kim loai trong Sir cd mat cua phan tu nudc lam giam dung dich loang bing phuong phap trie kha nang phat quang ciia ion dat hiem do quang va trong phan tach sac ki. Mdt sd sir chuyen nang lupng ciia ipn kim loai d P-dixetonat dit hiem ddng vai frd quan trang thai kich thich den lien ket OH cua frpng la tac nhan dich chuyin trong phfl nudc cd tan sfl dao dpng cao. Mdt each cdng hudng tir, frong y hpe , dupc iing hieu qua di giai quyit van de nay la thay dung di che t?o diflt phat quang cho cac the cac phan tii nudc nay bang cac phfli loai man hinh phang da mau voi gia tii phu frp cd hieu irng angten. Vi vay.
chiing tdi tiin hanh tdng hpp va nghien Cliu phiic chit hon hpp cila mpt sd dat hiim (Y, Pr, Sm, Eu, Tb, Ho) vdi naphthoylfrifloaxeton (TNB) va bis- pyridm.
2. THUC NGHIEM
Chung toi chua flm thiy tai lieu nao ndi vi qui trmh tflng hop cac phiic chat hfln hpp cua Y. Pr, Sm, Eu, Tb, Ho vdi naphthoyltrifloaxeton va bis-pyridm.
Viec tflng hap cac phiic chat nay dupc md phdng theo qui trinh tdng hpp phiic chit hon hpp 2-(2,2,2-Trifloethyl)-l- uidonat cua Eu, Sm \ di phen trong tai lieu [1].
2.1. Ting hop cac naphthoyltrifloace - tonat dat hiem
Hon hpp gflm 0,1 mmol naphthoylfrifloaxetonat dat hiem (LnTNB) va 0,1 mmol bis-pyridm (Bpy) frong 30 ml metanol dupc khuiy deu trong 2h d 50''C. Khi dung dich cdn khoang 5ml, phiic chit dupc tach ra.
Lpc. nia kit tua bang metanol va lam khfl d nhiet dp phdng. Mau sac ciia cac Bdng 1. Kit qudphdn tich hdm lugng kim
san pham dupc md ta trong bang 1. Hieu suit 70-80%.
2.2. Cac phvong phap nghien ciru Ham lupng ion dat hiem frong cac phiic chat dupc xac dinh bang phuang phap chuan dp complexon dua tren phan ling tao phirc bin ciia ion dat hiim vdi EDTA d pH » 5 va chit chi thi asenazo III.
Phfl hdng ngoai duac ghi fren may FTIR 8700, frong viing 400-4000 cm"', theo phuang phap ep vien KBr tai Vien Hda hoc, Vien Han lam Khoa hpc va Cflng nghe Viet Nam.
Phfl cpng hudng hi hat nhan 'H-NMR va ''C-NMR cda Y(TNB)3.Bpy dupc ghi tren may Bruker -500MHZ d 300K, dung mfli CDCI3, tai Vien Hoa hpc, Vien Han lam Khoa hpc va Cflng nghe Viet Nam.
3. KET QUA VA THAO L U A N 3.1. Kit qua phan tich ham lupng kim loai trong phire chat
Kit qua d bang 1 cho thiy ham lupng kim lo?i tinh theo cdng thiic gia dinh cua cac phiic chat tuong dfli phii hpp vdi ket qua xac dinh bang thuc nghiem.
logi trong cdc phiec chdt
STT
1 2 3 4 5 6
Cdng thiic gia dinh ciia phirc chit
Y(TNB)3.Bpy Pr(TNB)3.Bpy Sm(TNB)3.Bpy Eu(TNB)3.Bpy Tb(TNB)3.Bpy Ho(TNB)3.Bpy
Mau sac ciia phirc chat Trang
Xanh Vang nhat Hong nhat Vang nhat Vang nhat
Ham luong ion kim loai frong phiic chat (%) Ly thuySt
8,56 12,91 13,62 13,78 14,32 14,69
Thuc nghiem 8,54 12,90 13,59 13.76,.,*l
14'39,„1
14,68 H
3.2. Phd hdng ngoai
!f-.
' "'..
, > t - 1 .
(a)
Hlnh 1: Phd hdng ngogi: a. Eu(rNB)3(HiO)2
(b) b. Eu(TNB)3.Bpy.
Bdng 2. Cdc ddi hdp thu ddc frung trong pho hong ngogi cUa phuc chdt vdph6i tic ( u, cm'')
STT 1 2 3 4 5 6 7
Hpp chat Bis-pyridm Y(TNB)3.Bpy Pr(TNB)3.Bpy Sm(TNB)3.Bpy Eu(TNB)3.Bpy Tb(TNB)3.Bpy Ho(TNB)3.Bpy
VsO-H VsCH(Bpj+TNB)
3045 3067 3058 3055 3065 3058 3062
u c=o
1615 1612 1611 1613 1615 1614
VsC-F
1304 1298 1295 1296 1298 1296
VsM-O
581 570 574 577 568 575
Vs M-N
463 477 478 471 428 475
Trong pho hong ngoai cua cac phuc chat h6n hop khong xuat hien cac dai hap thu dac trung cho dao dong hoa tri ciia nhom OH trong vung 3000-3500 cm"', trong khi cac dai nay the hien rat ro trong cac phuc chat bac hai tuong umg, chung to nuoc da bi da>' ra khoi cau phoi tri. Cac
dai trong vung 3060-3109 cm thupc vh dao dong hoa tri ciia nhom =CH ciia vong thom napthalen ciia phoi tu TNB va bis-pyridin. Dai hap thu tai 1610-^1615 cm" dac tnmg cho dao dpng ciia nhom C^O cua TNB phdi tri. Cac dai trong vung 568^581 dupc qui gan
cho dao ddng hda trj ciia Uen ket M-O.
Su xuit hien ciia dai u M-N " ™ng 428-i-478 cm'' chiing tfl bis-pyridin da tham gia phoi fri vdi nguyen tii frung tam quaN.
3.3. Cong hirdng tir hat nhan Di nghien cira kl hem cau tnic ciia phiic chit, chiing tdi chpn mot phiic chat dai dien la phiic chat cua Y(III) de nghien ciru bing phuong phap phd cflng hudng tir hat nhan'H va "C.
Hinh 2 la phfl cpng hudng tir hat nhan ' H ciia phirc chat Y(TNB)3.Bpy, sir qui gan cac tin hieu dupc trinh bay d bang 3. Sfl
thir tu, ki hieu cac H cua naphtalen • phen dupc chi ra trong hinh 4.
"YiY ' w ' v
Hinh 2. Pho 'H-NMR ciia Y(TNB)3.Bpy
Bdng 3. Su qui gdn cdc tin hiiu trin phd 'H-NMR cita Y(TNB)3.Bpy
STT 1 2 3
4
5 6 7
Vitri (ppm) 8.40 7.93 9.48
7.76+7.88
7.51 7.44 6 47
Dac diem singlet doublet doublet
multriplet
friplet frip et
singlet
Tich phan 3,0 3,0 2,0
13,0
3,0 5,0 3,0
Qui gan 3H ciia3Ci 3H ciia3C5 2H ciia 2Cd 9H cua 3Cg, 3C4,
3 C3 va 4H cua 2Ca. 2Cb 3H cua 3C7 3Hcua C6va2H
cuaCc 3H ciia 3 nhdm C-H
Tren phfl cflng hudng tir hat nhan ' H ciia Y(TNB)3.Bpy, tin hieu smglet d 6,47ppm vdi ti le tich phan 3.0 dac trung cho proton cua dixeton dupc qui gan cho 3H ciia CH h-ong 3 phoi hi TNB. Cac tin hieu d 7,76 + 7,88 dac trung chp proton vdng tham, chiing tdi qui gan cho cac H
cua vdng naphtalen va vdng Bpy. 6 day cd su xen phu gitra cac tin hieu proton cua vdng naphtalen va vdng Bpy.
Viec qui gan chu yiu dua tren su phan tach cua cac tin hieu va ti le tich phan thu dupe. Nhu vay, tren phd cdng hudng tit hat nhan ' H ciia Y(TNB)3.Bpy ngoai cac
tin hieu edng hudng xuat hien nhu trong phfl cpng hudng tir hat nhan ' H cua Y(TNB)3(H20)2 cdn cd them cac tm hieu cpng hudng cila cac nguyen tu H ciia phfli tu Bpy.
De khang dmh them ve ciu triic cua Y(TNB)3.Bpy, chiing tfli su dung phuang
phap cflng hudng ttr '^C (Hinh 3, bang 4). Kinh 3: Pho "C-NMR cUa Y(TNB)3.Bpy Bang 4: Cac tin hieu tren phfl '^C-NMR ciia Y(TNB)3.Bpy
STT 1 2 3 4 5
Vi tri (ppm) 18 ,1 171,6 118,0 92,5 120,6*153,2
Dac diem Singlet Quartet Quartet singlet singlet
Qui gan
2C ciia C=0 nhdm xeton C cua CF3
C 11 cua C-H ciia xeton IOC ciia vdng naphtalen, 5C cua vdng phen
Tren phfl 'X-NMR xuat hien 19 tin hieu cdng hudng iing vdi bp khung cacbon cua phan tu Y(TNB)3.Bpy. Hai tin hieu d I88,lppmva 171,6ppm dupc qui gan chp 2 nguyen tu C ciia nhdm C=0. Tin hieu quartet d 118 ppm ling vdi C cua nhdm C-F, tin hieu don bpi d 92,5ppm irng vdi C ciia nhdm CH vung xeton. Cac tin hieu d 120,6-153,2 ppm dac trung cho cacbon vdng tham duoc qui gan cho 15 cacbon ciia vdng thom, frong do 10 tin hieu ciia
C vdng naphtalen va 5 tin hieu cua C vdng Bpy .Do viec qui gan timg tin hieu la phirc tap va khflng can thiet nen chiing tdi khdng qui gan cu thi timg tm hieu cho C cua vdng naphtalen va vdng Bpy.
Tir cac ket qua thu dupc bang phan tich nguyen td, phuang phap phd hdng ngoai va phuang phap cdng hudng tir hat nhan, chimg tdi dua ra gia thiet ve cdng thiic cau tao cua cae phirc chat (Hinh 4).
5 4
Hlnh'
(b)
Phiic chdt (a). Bpy (b). TNB (c) (c)
4. KETLUAN
Da tong hap dupc 6 phiic chat Ln(TNB)3.Bpy (Ln =Y, Pr, Sm, Eu, Tb, Ho), va nghien ciiu cac san pham thu dupc bang phuang phap phd hflng ngoai.
Da nghien ciiu phirc chit Y(TNB)3.Bpy bing phuong phap cpng hudng tir hat nhan ' H va "C. Kit qua cho thiy cd su phdi fri giiia phfli tir va cac ion kim loai qua cac nguyen tir oxi cua xeton va qua hai nguySn tu nita cua Bpy, phan hi Bpy da day cac phan hi H2O ra khdi cau phdi tri cua cac phiic chat bac hai.
L&i cdm on: Nghiin cuu ndy dugc tdi trg b&i Quy phdt triin khoa hgc vd cdng nghi quoc gia (NAFOSTED) trong de tdi masd 104.02-2011.31.
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