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TNG HP, XC NH CU TRC V TNH CHT HUNH QUANG MT S PHC CHT 1,10-PHENANTROLIN TECBI(III) Nguyn c Vng1, Nguyn nh Luyn2
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Trng i hc S phm, i hc Hu
Tm tt. Cc phc cht ca Tb(III) vi 1,10-phenantrolin v phi t hu c (CH3COOH, ClCH2COOH, Cl3CCOOH) c tng hp v xc nh thnh phn da trn phng php: phn tch nhit v phn tch nguyn t. Cu trc ca phc cht cng c xc nh bng phng php phn tch ph hng ngoi (IR). nghin cu tnh hunh quang ca cc phc cht v so snh tnh hunh quang gia cc phc cht nghin cu.
1. M u Phc cht ca 1,10-phenantrolin (Phen) vi mt s nguyn t t him c cc nc trn th gii nghin cu rng ri trong nhiu nm tr li y [8], c bit mt s phc ca Phen vi Eu, Pr, Sm c tnh cht quang hc nn c ng dng trong nhiu lnh vc nh trong nng nghip, khoa hc vt liu [3, 4]. nc ta, vic tng hp cc phc ca nguyn t t him vi Phen v mt s phi t khc cha c nghin cu nhiu v mi dng li phc ca Europi, Neodym. Trong bi bo ny, cc kt qu nhn c khi nghin cu mt s phc cht ca Tb(III) vi Phen v phi t hu c s c thng bo. 2. Phn thc nghim 2.1. Thit b, my mc - Ph hng ngoi ca phc cht c ghi trn my IMPACT-410-NICOLET trong vng 4000 400 cm-1 ti Vin Ha hc, Vin Khoa hc v Cng ngh Vit Nam. - Hm lng cc nguyn t C, O, N c phn tch trn my phn tch nguyn t Thermo Electron Eager 1112 ti Vin Ha hc cc hp cht thin nhin, Vin Khoa hc v Cng ngh Vit Nam. - Hm lng Tb2O3 c xc nh bi gin phn tch nhit TGA c phn tch ti Trung tm phn tch vt liu, trng i hc Bch khoa H Ni. 2.2. Tng hp phc cht - iu ch cc dung dch mu i Tb(X)3 [2]: Dung dch mui c iu ch trc tip t Tb2O3 99,9% (M) bng phng php sau: cn chnh xc lng Tb2O3 tnh
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ton trc khi chuyn vo cc chu nhit, thm t bng nc, thm t t dung dch axit c HX (X: CH3COO, ClCH2COO, Cl3CCOO) (PA) v un nng n khi tan ht, ri chuyn dung dch vo bnh nh mc. Thm nc n vch v lc u thu c cc dung dch mui tng ng c nng cn pha. Nng ca cc mui c kim tra li bng phng php chun bng DTPA 10-2M vi ch th l Arsenazo (III) trong mi trng m axetat c pH = 5-6. - Tng hp cc phc cht [6]: Ly 4 mmol Phen ha tan trong 50 ml cn tuyt i, sau cho phn ng vi 10ml dung dch mui Tb(X)3 0,2M, pH = 4,56. Hn hp phn ng c un nng n si v sau c ch ha vi 150ml axeton nng, yn trong 2 ngy, khi cc tinh th ca cc phc cht Phen-Tb3+-X- s c tch ra d i dng kt ta. Cc tinh th phc cht c lc v c ra bng axeton. Sy v bo qun tinh th phc cht nhit 50-80oC trong vi gi. 2.3. Phng php tnh hm lng Tb2O3 v thnh phn C, H, N trong phc cht Cn khi lng a(g) phc cht nghin cu a vo phn tch nhit n nhit cao phc cht khng phn hy c na thu c b(g) Tb2O3 (theo gin phn tch nhit), t tnh c %Tb2O3 trong phc cht. Thnh phn % cc nguyn t C, N, O trong phc cht thu c t kt qu phn tch hin th my phn tch ca phng phn tch nguyn t. 3. Kt qu v tho lun 3.1. Hiu sut tng hp mt s phc cht 1,10-phenantrolin Tecbi(III) Qu trnh tng hp phc vi nhng t l mol khc nhau gia ph i t Phen v Tb(III) l: Phen:Tb = 1:1; 2:1;3:1; 4:1, kt qu nghin cu c ch ra bng 1.
Bng 1. Hiu sut tng hp phc Tb(III) vi Phen cc t l mol khc nhau
1 2 3 4
Kt qu nghin cu bng 1 cho thy phc [Phen-Tb3+-CH3COO-] (P1) v phc [Phen-Tb3+-CH2ClCOO-] (P2) t l (mol) Phen:Tb3+ = 1:1 cn phc [Phen-Tb3+Cl3CCOO-] (P3) t l Phen:Tb3+ = 2:1 cho hiu sut tng hp l ln nht, tng t nh phc ca Eu [1]. T l ny c chn tng hp phc cho cc nghin cu tip
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theo. Phc cht tng hp c c mu tm, dng tinh th v d tan trong axit long. 3.2. Xc nh thnh phn phc Thnh phn phc c xc nh bng phng php phn tch nhit v phn tch hm lng cc nguyn t C, O, N qua cc gin hnh 1.
(a)
(b)
Hnh 1. Gin phn tch nhit (a) v phn tch nguyn t (b) ca phc [Phen-Tb3+CH2ClCOO-]
T gin phn tch nhit, ta xc nh c nhit bt u phn hy ca phc cht n nhit phc cht khng phn hy na, xc nh c bn ca phc cht v khi lng ca Tb2O3 theo gin , t tnh c % Tb2O3 theo khi lng phc cht a vo phn tch nhit. T gin phn tch nguyn t kt qu tnh thnh phn % cc nguyn t C, O, N thu c t my phn tch. Cc s liu so snh hm lng Tb2O3 sau khi phn hy phc, v phn tch nguyn t thnh phn phn trm cc nguyn t C, O, N trong phc gia s liu tnh ton theo l thuyt (%LT) v theo kt qu phn tch c (%PT) bng 2.
Bng 2. Hm lng Tb2O3 sau khi phn hy phc v thnh phn C, H, N trong phc
K hiu P1 P2 P3
Hp cht Phen-Tb3+-CH3COOPhen-Tb3+CH2ClCOOPhen-Tb3+-CCl3COO-
T bng s liu trn cho thy kt qu gia l thuyt v thc nghim tng ng nhau. T , kt lun thnh phn phc tng hp c ph hp vi cng thc gi nh theo l thuyt l PhenTb(OCOCH3)3, PhenTb(OCOCH2Cl)3 v (Phen)2Tb(OCOCCl3)3.
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3.3. Xc nh cu trc phc cht bng phng php ph hng ngoi Ph hng ngoi ca Phen v phc PhenTb(CH3COO)3 c trnh by hnh 2, s sng c trng ca cc cht c ghi bng 3.
(b) (b)
(a)
(b)
(b)
Hnh 2. Ph hng ngoi ca Phen (a) v PhenTb(OCOCH3)3 (b). Bng 3. Cc bc sng c trng trong ph hng ngoi ca Phen v cc phc cht
C H
(thm)
C-C ; C-N 1619; 1584 1600; 1554 1591; 1565 1601; 1508
COO
(x)
C=O(-COO) 1384
Phn tch chi tit cc ph dao ng hng ngoi cho thy, trn ph IR ca phc cht khng c dao ng ca nhm OH ca H2O (O-H = 3391cm-1), iu cho th y phc cht khng c H2O trong phn t. Kt qu ny ph hp vi kt qu phn tch thnh phn nguyn t. iu chng t Phen y nc ra kh i cu ph i tr khi lin kt to phc. Ph hp th hng ngoi ca ph i t Phen - (C12H8N2.H2O) c nhiu vn ph. Mt s vn ph quan trng c nhn dng nh sau: O-H = 3391cm-1, C-H(thm) = 3062cm-1, C=C = 1619cm-1, C=N = 1584cm-1 [7]. Khi hnh thnh phc cht, vn ph C=C, C=N thay i (bng 3). S chuyn dch xung tn s thp chng t phi t Phen lin kt vi ion trung tm Tb3+, c th hnh thnh lin kt ph i tr N(Phen)Tb. Kt lun v s chuyn dch tn s dao ng ha tr ca lin kt C=C, C=N trong phn t Phen xung tn s thp l do hnh thnh lin kt ph i tr ca N vi ion kim loi trung tm. Nh vy, trn ph hng ngoi ch ra dao ng ca cc nhm c trng c trong phc. Trong phn t cc phc cht, phi t Phen lin kt vi ion trung tm Tb3+ qua 2 lin kt phi tr N Tb(III) v hnh thnh vng cng 5 cnh.
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Cc ph i t axit axetic v dn xut clo ca chng trong phc cht dng anion. Cc phi t CH3COO- v CH2ClCOO- lin kt vi ion trung tm bng hai lin kt ph i tr qua hai nguyn t oxy ca nhm -COO- to vng cng 4 cnh. Ring ph i t CCl3 COO- lin kt vi ion Tb3+ bng mt lin kt TbO(-). Qua vic phn tch cc phc nghin cu chng ti ngh cc lin kt c to thnh trong phn t cc phc cht nghin cu sau:
N N
H
N
O Cl O
C-C Cl
O C-C Tb H H H C-C H H
H H N Tb O Cl C-C O O C-C Cl N O O C-C
Cl H H
Cl
N Tb O
Cl
H C-C H H
O O O O
O C-C
N
Cl Cl
Cl
C-C Cl Cl
H H
PhenTb(OCOCH3CH3)3
PhenNd(OCOCH2Cl)3
(Phen)2Nd(OCOCCl3)3
3.4. Nghin cu tnh cht hunh quang ca phc cht Ph hunh quang ca cc phc cht P1, P2, P3 c trnh by hnh 3
0.25
M2
0.40 0.35
M3
1.0
M1
0.20
0.30
0.8
Cng (vt)
Cng (vt)
0.25
0.15
Cng (vt)
400 450 500 550 600 650
0.6
0.10
0.4
0.05
0.2
0.00
0.00 -0.05
400 450 500 550 600 650
B c sng (nm )
Bc sng (nm)
Bc sng (nm )
Qua hnh 3 cho thy, ph ca cc phc cht nhn c c 4 nh c trng ti cc bc sng 488 nm, 554nm, 582 nm v 617 nm ng vi cc chuyn mc 5D4 7F6, 5 D4 7F5, 5D4 7F4 v 5D4 7F3. ca ion Tb3+, bc sng 554 nm l im nh pht x mnh nht. Da trn s nng lng ca Tb3+, c th a ra c ch truyn nng lng gia ion Tb3+ nh sau: cc ion Tb3+ trng thi c bn, sau khi hp th photon ti bc sng 400 nm s chuyn ln trng thi kch thch c mc nng lng cao hn, sau hi phc khng pht x v cc mc nng lng thp hn (5Dj, j= 2; 3; 4) v cui cng l hi phc pht x v cc mc nng lng c bn (7Fj, j = 0-6). Trong ph kch thch xut hin cc vn ph, c quy c bng nhng cu hnh bn trong dy chuyn tip f-f ca Tb3+ bng cc lin kt chuyn tip nhng nng lng ca phn t phen n Tb3+. Tn ti hiu ng chuyn ch ca nng lng t phn t phen n ion Tb3+ th ion ny c cng khuch tn trong vng
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ph 488 - 617 nm. Cc phc cht nghin cu u pht quang v cng pht quang ca cc phc cht cha hai phi t phen ln hn phc cht cha mt phi t phen. Mt khc, nu hai phc cht u cha mt phi t phen hoc u cha hai phi t phen th phc no c ph i t l gc ca axit mnh hn s c cng pht quang mnh hn (tnh axit yu dn theo dy: CCl3COOH > H2CClCOOH > CH3COOH). Vy cng pht quang ca cc phc cht yu dn theo dy: (phen)2Tb(CCl3COO)3 >phenTb(CH2ClCOO)3 >phenTb(CH3COO)3. Mt khc chng ta thy rng ph hunh quang ca phc phenTb(CH2ClCOO)3 v phenTb(CH3COO)3 gn ging nhau v khc ph hunh quang ca phc cht (phen)2Tb(CCl3COO)3 iu ny khng nh thm v cc lin kt ngh trong cc phc cht. 4. Kt lun - tin hnh tng hp phc cht ca Tb(III) vi 1,10-phenantrolin v ph i t hu c, nghin cu v t l s mol gia ph i t Phen vi Tb(III), kt qu thu c cho thy hiu sut tng hp t gi tr cao nht ng vi t l mol Phen: Tb(III) = 1:1 i phc cht P1, P2 v 2:1 i phc cht P3. - Thnh phn phc cht c xc nh bng cc phng php phn tch nhit v phn tch nguyn t, cc lin kt trong cc phc cht c xc nh bng phng php vt l hin i IR. - xc nh tnh cht hunh quang ca cc phc cht: (phen)2Tb(CCl3COO)3 , phenTb(CH2ClCOO)3, phenTb(CH3COO)3, so snh tnh cht hunh quang ca cc phc cht.
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[5]. A. S. Alikhanyan, I.A.Solonia and M.N.Rodnikova, Thermodynamic stability of neodyminum nitrate complex with 1,10-phenanthroline, Russian Journal of Coordination Chemistry, Vol.52, No.8, (2007), 1220-1222. [6]. Fmelby By. L.R., Rose N.J., Abramson E. and Caris J.C., Synthesis and fluorescence of some trivalent lanthanide complexes, J. Am. Chem. Soc, Vol 86, N0 23, (1964) 51175124. [7]. Hart F.A. and Laming F.P., Complexes of 1,10-phenanthroline with lanthanide clorides and thiocyanates, J.Inorg. Nucl. Chem, Vol. 26, (1964), 579-585. [8]. Minbo Chen, Zongsen Yu., Rare earth elements and their applications, Metallurgical Industry Press, Beijing, 1995. [9]. S.V.Larionov, V.L.Varand, R.F.Klevtsova, T.G.Leonova, L.A.Glinskaya and E.M.Uskoy, Synthesis of Heteroligand Complex Nd(phen){(iso-C4H9)2PS2}2(NO3). Crystal Structure of Nd(phen){(iso-C4H9)2PS2}3 and Luminescent Properties of these Compounds, Russian Journal of Coordination Chemistry, Vol.34, No.12, (2008), 931-937.
SYNTHESIS AND DETERMINATION OF STRUCTURE AND FLUORESCENT PROPERTIES OF SOME COMPLEXES OF 1.10-PHENANTROLINE AND TERBIUM(III) Nguyen Duc Vuong1, Nguyen Dinh Luyen2
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Abstract. The complexes of Tb(III) with 1.10-phenantroline and organic ligands (CH3COOH, ClCH2COOH, Cl3CCOOH) have been synthesized and characterized based on thermal and elemental analysis. The structures of the complexes were determined by infrared spectra (IR). The complexes were also compared in terms of fluorescent properties.