Tgp chi phdn tich Hoa, Ly vd Sinh hgc -Tap 19, Sd 1/2014
TONG HOP VA NGHIEN CUtJ PHlTC CHAT CUA Cu'*, Ni'* va Zn'* VOII PHOI Tiy CHITA NHAN ANTRACEN
Din tda sogn 28-11 - 2013
Nguyin Minh Hiii, Dinh Thj Thao, Lira Thi Quynh, Nguyen Himg Huy Khoa Hda hgc, Truang Dgi hgc Khoa hgc Tu nhien, Bgi hgc Qudc gia Hd Ndi
SUMMARY
SYNTHESIS AND CHARACTERIZATION OF Cu'", Zn'" and Ni'* COMPLEXES WITH ANTHRACENE-CONTAINING LIGAND
This work reports the synthesis and characterization ofCu , Zn and Ni complexes with l,2-bis[(anthracen-9-ylmethyl)aminofethane. Herein, two ligands were synthesized: l,2-Bis[(anthracen-9-ylmethylen)aminofethane (BAAEl) and 1,2- Bis[(anthracen-9-ylmethy)aminofethane (BAAE2). BAAEl was synthesized via condensation reaction between ethylenediamine and anthracene-9-carcbadehyde, which was then reduced by NaBH^ in methanol to give BAAE2. The complexes were prepared fi'Om acetate salts of corresponding methanol ions and BAAE2. The formation ofthe
compounds was investigated by IR. NMR and MS spectroscopy.
Keyword(s): Antracen. hgp chdt phdt quang, phirc chdt kim logt chuyen ttep.
I . M O D A U quang li dac biet. BAAE2 la phdi tir hai Antracen la mdt hidrocacbon da vdng ctog chira vdng antracen cd kha nang tham va la mdt hgp chit cd kha ntog tham gia phto ling tao phiic chit vdi phat huynh quang. Vi vay antracen va mudi axetat ciia cac ion kim loai chuyin cac dto xuat cua nd ddng vai trd quan tilp Cu'*, Zn'* va Ni'*[4, 5]. Bai bto nay ttgng ttong Unh vuc vat lieu phat quang nghien ciiu su tdng hgp va xac djnh clu nhu nguyen lieu cho den laser, diot phat tnic ciia cac phiic chit tten.
quang hay cac thilt bj phat stog va ttong 2.THU'CNGHEM
ngtoh cdng nghiep thuc phim. dugc 2.1. Hoa chat va cac phu-ffng phap phara hay ndng nghiep.. [1-3]. Phiic nghien cirn
chat cua phdi tu chiia hgp phin anttacen Tit ca cac hda chat cd do tinh khilt dugc mong dgi se thi hien tinh chit phto tich: Anttacen-9-cacbandehit,
etylendiamin, natri bohidrua, axeton, metanol, dietyl ete, diclometan, n-hexan va D M F . Phd hdng ngoai (InftaRed specttoscopy-IR) dugc do tren may Impact 410 - Nicolet (My)theo phuang phap ep vien bing KBr. Phd cdng hudng tir hat nhto ' H - N M R (Nuclear Magnetic Resonance-NMR) dugc ghi tten may FT -NMR vdi dung mdi la CDCI3. Phd khdi lugng MS (Mass Specttometry) dugc ghi ttSn may LC- MSD-Trap-SI vdi dung mdi la metanol.
Cacphuong phap IR, ' H - N M R va MS dugc do tai Vien Hda Hgc-Vien Khoa hgc va Cdng nghe Viet Nam.
2.2. Tong hgp
2.2.7. Tong hcrp I,2-Bis[(antracen-9- ylmetylen)amlno]etan (BAAEl)
Anttancen-9-cacbtodehit (l,94mmol) dugc hda tan ttong DMF/CH3OH (1:5, v/v). Etylendiamin (0,97 mmol) ttong metanol dugc them vao dung djch tren.
Hdn hgp dugc khuiy va dun hdi luu ttong 4h. Phin ket tua mto vtog dugc lgc, nia bing metanol va dugc Itoi kho frong binh hut Im. Hieu suat phto ling dat 86,0%.
2.2.2. Tdng hgp l,2-Bis[(antracen-9- ylmetyl)amlnofetan (BAAE2)
BAAEl (0,907 mmol) dugc hoa tan ttong CH2CI2/CH3OH (ti le thi tich 2:1).
NaBHi (3,9 mmol) ttong metanol (3 ml) dugc them vao dung dich tren. Hdn hgp dugc khuay qua dem d nhiet do phdng (ttong dilu kien tdi). Phin kit tua mto vtog dugc lgc, nia nhieu lto bing nudc cat va dietyl ete, sau dd dugc Itoi khd trong binh hut toi. Hieu suat phto itng dat 80,5%.
2.2.3. Tdng hop phiec chdt v&i phdi tir BAAE2
I- M(0COCH3)JiH2O
- c
Phdi hi BAAE2 ttong CH2CI2 dugc them vao dung djch mudi axetat cua cac kim loai tuong irng ttong metanol (ti le moi 1:1). Hdn hgp dugc kh^y ttong 3h (d dieu kien tdi), sau dd them n-hexan de thu lay ket tlia. Ket tua dugc lgc, rira btog nudc cit va dietyl ete, sau dd dugc Itoi khd ttong binh hut toi. Hieu suit phto ling: Zn(BAAE2) 71,5%, Ni(BAAE2) 64,4%, Cu(BAAE2) 75,2%.
3. KET QUA VA T H A O L U A N Phdi tu BAAEl dugc tdng hgp dua tren phto ling ngung tu giira anttacen-9- cacbandehide va etylendiamin vtii hieu suit cao (80,6%.). Vi phto ling nay cd bto chat la thuan nghjch nen BAAEl dugc khli hda btog NaBH4 de thu dugc BAAE2 chira lien kit don C-N bin virng (hieu suat: 80,5 %). Hai phdi tir deu
chua vong antracen kem ben vai anh sang nen cac phan ung duac tien hanh trong di^u kien t6i. Phoi tu duac tao thanh co mau vang nhat va tan tot trong cac dung moi huu ca nhu CH2Ci2, CHCI3, DMF... Ban d4u phan iing tao phuc giijra phoi tu BAAE2 \a muoi axetat khong hinh thanh ngay k^t tua ma chi xudt hien khi n-hexan dupc them vao.
Phuc chat thu dupc tan tot trong CH2CI- 2va il tan trong metanol. Mau s4c tuong ung cua cac phuc chat Zn(BAAE2), Ni(BAAE2) va Cu(BAAE2) la vang, xanh va xanh lam.
3.L Nghien cvu bang phirong phap pho h6ng ngoai
Tren pho hap thu hong ngo^i cua BAAEl (Hinh 1) khong con dai h^p thu manh ciia nhom cacbonji trong antracen- 9-cacbandehit a 1820-1660 cm'' ma xuat hien them dai hap thu iing vai nhom imin -C=N- 6 1636cm''. Dieu nay chiing to phan ling ngung tu giua antrancen-9- cacbandehit va etylendiamin da xay ra.
Su hinh thanh ciia phoi tu BAAE2 tir phan ling giGa BAAEl \'a NaBH4 dupc khang dinh bod su bien mat cua dai hap thu dac trung ciia lien ket -C=N- trong phdi tu BAAEl (Hinh 2).
Hinh 2. Phd hdp thu hdng ngogi cua BAAEl
Bdng l.Bdng guy gdn gid tri phd hdng ngogi cua BAAE2 vd cdc phuc chdt.
Hop chat
BAAE2 Zn(BAAE2) Ni(BAAE2) Cu(BAAE2)
(cm-') 1100 1107 1040 1074
^coo- (cm-')
1591 15S3 1574
' ' N 4 1
(cm-') 1622 1662 1662 1601
Hmh 1. Pho hdp thu bong ngoqi cua BAAEl
Tren pho IR cac phiic chat cd su xuSt hien dai hap thu ciia ion axetat d viing 1600-1550 cm"' chung td cd su tao phiic giira phdi tii vdi mudi axetat ciia cac kim loai tuong (ing (Btog 1).
Khac vdi phiic chit Zn(BAAE2) va Cu(BAAE2), fren phd hip thu hdng ngoai cua phirc chit Ni(BAAE2) xult hien dai hip thu d 3400 cm"' dac ttimg cho dao ddng hoa ttj cua nhdm OH trong phto tix H2O (Hmh 3). Nhu vay, nudc cd the da tham gia tao clu phdi tti cua ion Ni . Trong khi dd dai hip thu ung nay tten phd cua phirc chit Cu(BAAE2) va Zn(BAAE2) cd cudng do rit ylu ho?c gto nhu khdng dtog ke (Hmh 4 va 5).
Hinh 3. Phd hdng ngogi cua phuc chdt Ni(BAAE2)
Hinh 4. Phd hdng ngogi cua phiic chdt Cu(BAAE2)
Hinh 5. Phd hdng ngogi cua phuc chdt Zn(BAAE2)
3.2. NghiSn ciru b^ng phmmg phap cong hirong tv hat nhan ^H-NMR Phan tu BAAE2 co 28 proton nhung tren ph6 cpng huang tir hat nhan chi xuat hien 7 tin hieu. Dieu nay duac giai thich boi tinh doi xiing cua hop phan antracen va etylendiamin (Hinh 6 va bang 2).Cac tin hieu nay xuat hien a hai vung: vung truang thap (8,37-7,74 ppm) ung vai cac
proton tham cua hgp phan antracen va vung truang cao (4,7-2,11 ppm) iing vai cac proton no ciia hpp phan etylendiamin.Ngoai ra, tren pho xuat hien tin hieu smglet gi3n rpng a vung truang cao (2,11 ppm) dupc qui gan cho proton cua nhom N-H. Dieu nay dupc giai thich bai hien tupng lat ngupc cau tnic chop tam giac cua nguyen tii N.
Bdng 2.Bdng quy ket cdc tin hieu pho 'H- NMR cua phdi tuBAAE2.
STT 1 2 3 4 5 6 7
5{ppm) 8,37 8,26 7,96 7,44 4,70 3,16 2.11
Do bpi Singlet Duplet Duplet Multipiet
Singlet Singlet Singlet
Tich phan 1 2 2 4 2 2 1
Quy gan 2H(H,„) 4H (H,.,) 4H(H,,5) 8H(H2j,6,,)
4H (CH,) 4H (Cfl,) 2H (-NH-)
Bdng 3. Bdng quy kit cdc tin hieu phd 'H- NMR cUa phitc chdt Zn(BAAE2)
STT
1 2 3 4 5 6
7 5(ppni)
8,42 8,25 8,00 7,50 4,97 2,75
2,16 D6b6i
Singlet Duplet Duplet Multipiet
Singlet Singlet
Singlet Tich phan 1 2 2 4 2 2
4 Quy gan
2H(H,„) 4 H ( H , s ) 4H(H4 5) 8H(H3,3 6 7|
4H (C//,) 4H (CflJ 2H (-NH), 6H(-CHj)
• U "
f ^
'
a)
lli
i M B
k 4
1 . . i
* ' ' " " "
Hmh 6. Pho 'H-NMR cua phoi lit BAAE2
Tren phi 'H-NMR cua phiic chat Zn(BAAE2) cac tm hieu iing vdi cac proton thom ciia hgp phto anfracen hiu nhu khdng thay ddi nhieu so vdi cua phdi tu (Hinh 7 va btog 3). Hai tin hieu singlet gito rgng d 4,9 ppm va 2,8 ppm vdi ti le tich phto la 2:2 dugc quy gto cho proton no ciia hgp phto etylendiamin, cho thay sg tao phuc linh dgng cua phdi tii BAAE2 vdi Zn^'*".Tin hieu singlet d 2,1 ppm vdi ti le tich phto la 4 dugc quy gto cho proton ciia nhdm N-H va nhdm CH3 - cua ion CH3COO', chiing td ion nay da tham gia cto phdi tti. Do dd ion Zn^'^da tao phiic \m phdi hi BAAE2 dang hai ctog va hai ion axetat. Tuy nhien clu tnic cua phiic chatZn(BAAE2) cd thi la tu dien hoac vudng phtog. Do phli tu BAAE2 cd cto fruc cdng kinh va rit linh dgng nen phiic chit Zn(BAAE2) dugc gia thiet tdn tai d dang ni dien (Hinh 8).
1 ^k^"^^-^ i
1
1 a)
i Li ,*
i i|i-h' • : u 1
, t " « » OCOOi^
.. ^x.._
wy
Hmh 7. Pho 'H-NMR cua phirc chdt Zn(B,4AE2)
Zn
J "OCOCHs^ //
^ CH3COO ^ — / Hinh 8. Cdu Iriic gia dinh cua phirc chd!
Zn{B.i.4E2)
So \(t\ pho ' H - N M R cua phoi tu BAAE2, cac tin hieu cua phirc Ni(BAAE2) co dp phan giai kem. gito rgng va bi djch chuyen manh (Hinh 9). Cac tin hieu hi chdng chap len nhau hoac lto vao cac tin hieu dircnig nen. Dac biet, tin hieu d viing trudng thap ^14 ppm cd the dugc quy gto cho proton cua phan tu nudc. Vi va\.
cd the gia thiet rtog phirc chat Ni(BAAE2) co tinh thuan tir va khong ton tai o dang \-udng phang do cd su tham gia phli tri ciia H2O (Hinhl 0). Ket qua naj phii hgp ^•6i kit qua nghieii cii-u btog phuong phap pho hong ngoai
(Tren phd hdng ngoai cua phuc chat Ni(BAAE2) quan sat thiy dai hip thu cua nhdm OH ttong phto hi HjO).
Hmh 9. Phd H-NMR cia phuc chit Ni(BAAE2)
Hmh 10. Cdu true gici dinh cia phuc chdt Ni(BAAE2)
3.3. Nghien cmi phiic chat Zn(BAAE2) bing phtrong phap ESI-MS
Tren phd khdi lugng cua phiic chit Zn(BAAE2) khdng quan sat thay mtoh ion phto ttr [Zn(BAAE2)]* ma chi quan sat thay su xult hien ciia cum pic cd cudng do manh nhat d m/z = 441.25.
Khotog each giira cac pic ddng vi la 1 nen mtoh ion cd dien tich -t-l (z = 1). Cum pic nay dugc quy gto cho ion [BAAE2 + Hj"
Dieu nay chi ra rtog frong dieu kien ghi phd, phiic chat Zn(BAAE2) bj pha vd va phdi tir BAAE2 da bj tach ra tao thtoh mtoh ion [BAAE2+H]*. Ket qua nay phu hgp vdi su tao phuc chat linh dgng cua phoi tli dugc chi ra fren phd ' H - N M R .
4. KET LUAN
Hai phdi tti chiia vdng thom antracen BAAEl, BAAE2 da dugc tdng hgp. Phdi tu BAAE2 dugc sir dung de tao phiic chat vtii Ni ^, Cu^"*" va Zn^^.Cac ket qua phd hap thu hdng ngoai, phd cdng hudng tir hat nhto, da xac nhan phdi tu BAAE2 da tao dugc phu:c chat dang hai ctog vdi cac ion kim loai cimg vdi ion axetat. Zn(BAAE2) va Cu(BAAE2) dugcgia thiet tdn tai d dang hi dien do su cdng kenh ciia phdi tir. Ni(BAAE2) dugc gia thiet cd them H2O ttong cto phdi tti dto den tinh chit thuan tir cua phiic chit nay.
Ldi cam on: Nghien ciru ndy dugc tdi trg boi Tru&ng Bgi hgc Khoa hoc Tu Nhien - BHQGHN. Ma sd TN-13-11.
TAI UEU THAM KHAO
1. Dtog Nhu Tai, Nguyen Minh Thao, Ngu}'en Dinh Thtoh, "Baza azometin va cac sto phtoi chuyen boa. XI- Tdng hgp va tinh bazo cua cac azometin day 5- amino-2-metylindol",7'tip chi Hod hgc, 24, tt.19-20 (1986).
2. G. Zhang, G. Yang, L. Yang, Q. Chen, J.-S. Ma,"Synthesis, Characterization and Photophysical Properties of Novel Dinuclear Silver (I) and Mononuclear Palladium (II) Complexes with 1,2 Bis[(anthracen-9-lmethyl)ammo]ethane", Eur. J Inorg Chem, 10, pp.l919-I926 (2005) (xem tiip tr. 73)
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