New Pyrazoloquinolin€s and their application in or8anic

New Pyrazoloquinolin€s and their application in or8anic

LWĄUo\D 'N| lR,/l
KA REN
cH \cŻ^TR
q\Flnl
lAN'
ANDRŻE| DA
N
EL"
New Pyrazoloquinolin€s and their application in or8anic
light-emitting diodes with po1y(N-vinylcarbazole) matńx
sumnaty Tlrele
(PAQ) dosdib
\'olo śynrhcsizcd sn ncw Pylab]ogulnolilrc deńvaiivs
a lońula (l), i]r which the neanings of & subsituent
'!ith
oc/,rrr, .crrr, -H, .ocHr, -cl. The n
dhraĆfur'ed. among othcE, o| ih" b""i".f,H NMR"p-h ńd
"l.*.t^l
analyss .cs!]b' Mirhlr6 of ihesc PAQ d€rivativ* $'jth poly(N vińylc'rbijn
zol.) vcrc iPplicd
ihe otgłli.li8hr emitrińs djodcs (LED)' sPecE ofab.
sorption' Photolunimsem. {FL) and c|.dlo|uńlnesen..(EL) of LEDS PI?.
parcd were Pte*trhd' Il ]i3s beń fould that the lyPe of Ę subshtueni n]n!
cn.ś PL łnd ELqMntum yields
Ke]' {ords: pyn2ljloguinolnr. dcrivłlivc' PoIy(N vinylcalbazo]e), otg.nn
ts!
"r, Td.J..Pho,oL,r
Polynsituorg riclight omitti,Edn es(LED)irc
b.licvcd io bc an altdnativĆ b tid lonilcat]rodc m],
iubcs in rhe appli.atio's Lvhich sr)ourd combinc cL.ap
Flicc ind good imagin8 pi(,P.łics Th. mośimPo int
Fit of such kikl Óf dĆvfc n lhc cnEsn( h],el wli.h il
ciih.r Polvmol or low moL..u1.r oĘłni. hatelial
(nin&r as dy! o! .hlonophorc) i
oftcn a .onbinidon of boih is us
blcnd' su.h olg n. LED ilwł)'s lr a Iaydcd śru.turc
cithcr eI.dro|-donilin3 or elechon-łc.cPlin3 side
groups. Thc cl.ctoopti.al propcrtics oI PAQ .hiomo
phoros rvsc icsbd in the brcDds wiih poly-N vinykar
bazol.olVK) matii This nrbix k tłnspal.nr rh.
Eoodfilmfomijr!
ahility rnd hi8h lhsmal śability
good holcs .oMuctor but on ih. Óthlr band its own bIU.
ELqu run vicrd is for ioo low b
qu trcme| B Thc łdd ilion of a s! iiiblc chrcmoPhore int)
PvKńaEn ]mpmv* l]LPfuPc icsand8h.satr oPPor
ttr'ily b fune tllĆ colour of cniilcd lighł Imn vrlct b
Ertcn ln ihc fufore sonc of.hcen PAQ chrońophorcs
E llbc dre' \ sEncd o rfo P!'K.h.nn i, nbh' I i purc
Pol'nfi ńlhni whLdl \d\cr tohJn.lLLhAiń.l Ęł\
naieriib (lhc anod. js usually t xPar.na
Thc clc.horumirEscak (EL) orcua who rhc positive
ald nc8a liv. .h als. c'EicĘ irc injcdcd iŃo ł dlinfilń
oI emksilc lavcI' thcn fonn ilr. lxĆilon sbts which r..
cońbiń..mithn8 ihcliEht' Th. detailcd dcsriPtion o1
i'rcycnŃ in polym.l
cls.wh.r n,2l Al
i]tDgh LEDS hŃ. bei
b'N
l'+'lollNol'NEsDERlvŃtvE'PRo.AnAT'oN
^
śdeca'lc 13l, thrrĆ n
{ill mpo łntd.n rd lorn cliikshowiĘ intcńs.
Th! frośnnPo łnt svnihch. method of ]H PyIi.
.mńsiotr i'] tlE blu. slc.ti] qion tÓ Pfutucc IUll..o' z.Id3, ł'dquinolńcs dcriv ives l
'
lou] f] d kPla)'s Th. dcriva tivc
ol r r] pvrł?olol:r, łr1] ths r{l is Fricdiindcr mndeB
quinolinś (PAQ) alc Potc|tii] mndidates fo! thc bh'c ful.J p]łazol3 oncs with anthraniliĆ ald.hydc lequ}
]ight e]e.to|!mńscni materiarś |+7l
hon(1)l TheĘachonu$'allyi!6llicd outintncmc]iol
Tlis work dcsoibes ihc svnrhcsis d .haracreri
irr dierhylcnc gty.ot. sim!
ildchvdes and
'nthranih.
L troPe*iś of a ncs'
}ami''obcnzophenone5 ind
łcctoPh.non.s łre nor
rcadiryiliilabledErsctions oI5.
Żoles l3l or 4{lo]'l'{hlomPynzol.s l9l wth subni_
tutcd nlineslĆquation(2)lwercaPFlildforth.synthc
rt]ńduchvc
dłjYahvs Due to theś.l6chons ihc modi
ljd hom of o tbo(.ljc Iij]g łte loty .asy'
This n.thod sulleE .eńain lińibhons ind disid
vł nlłges h5 aPpl icaiion lor Pl.PaF tion o t 'l'iryl dcriv.
iivcs is testictd by ihc alłilabiliry of 2
'nlno'bcnzo_
ses oJ PAQS
"CIx"
c*:
t"ł' _ oir':
lins wasdevclolEl in our home litrontor_v nll lcqui.
6on (a)l. tsrc ly 1ł.ilji es lhc no,jification of thc łrG
ńah. nng in th. position 4 (witl
hchrocycliĘ rin& bo). TrE d.sĆt
]owed b syŃh*ize of rhe cnlońÓPhote! bein8
thg sub
synńesis ol PAQS derivatjveŚ
DePeńdĘg on lhe l.tcral grcup to lrc subśihtc, onc
thr* describBi bclow ncthods of i synthcsis w
lsod T1'. gcnnłl sfuclurc ol lhe synihciŻcd P^a!
de,ivativcs is shown ir Fornula 0) r,riheFonnnra o)R
ńcals Pńenyl group (Fh)' R: methyl grouP {Mc),
R]_Ftolyl3roup (łcH1coH', while Rr gronp hm
valious rełnin8s, a5 follo s: Br GamPlq PAQr),
-ocóH5 (PAQz), ocHl olAQ3)' l' ojAo1)' c'jJ
ol the
*ńt
Thc .omPounds PAQ4 and PAQ5 w.ic PIcPłrcd by
.ondcnsalion Plo]yl aldehyde q'ith słaryl)amirc.3_
.neihyl 1 phenllpr'lazolc in ihepreseie olaihydn!s
PhenoB and aroylPynrclcs U€U any a ńlxilEP syn
m€ młtcdłlPrcPalahon'
the9iŚ n r.qlired
PAOr, PAQą PAQ3, and PAa6 wcrc prcparcd by.on.
'or
ińProvAt
synthesis of 4'łryl.]H_P}Tł drnsabon oi 3'm.thyll-phcnyl-4.(p.ncthylphcnylj.
lkcntl'
'n
has be.onc availablc from aro
zolÓF, a
dcne)Pyńzolln_5.onc wiih $'bsliiutcd riliIś|cqu}
'hlinolines
maiic anins with 4 benzylidene pynzolo.3-ones nol hon (3)Iusi$ei$łÓnv.ntionalhlatiĘ ormiĆtowav!
lquaiion (3)l Jud ĘĆently on.poi synihAis (hree ilEdiłtion l10l' All Óf the ĆÓńpolnds (!x!tpt PAQ4)
.onpon€nl rel.tion) of +aryl il' pyrazo]ol3, ,I l']9ui'1o
w.re also preparcd palilclly by th
iion le']Uation 1ł)l of alońah. a
3
m.thyLr phcnylPylłzoIiF5_oncl11l
charłdeliŚtic o' PAQs d.ńvatives
4.(4|MethylPhĆnyl)
3
nłh]rl ]
phrn]rl
lH pyrazolo
YgnÓ\{ Ćlystals' 32 f, nclhng poi] (ił l] ) = 206_
207oc ł Gydohexane) = 437 Dn HNMR(3ooMHł
cDc\):3.s1 (2H,/, l=3.7H2,2' H,61H),3 2r OH, J,l=
9.o5 Hz,3-H),7.75 nH, n,I = 8.7 rrz,5 H),7.74 (1H, t,I =
3 65 Hz, 6-H), 7.s6 (2H, r, I = s0 I12,3'H, 5'H),
7 3Ż_7Az|1Ąn),3 H),7 4(ŻH, d,] = 3'0IŁ' 3' H, ] tl),
7':r4l2H,,1, l = 3 0 tsL' 2' ts' 6'.H)'7 Ż:] |lH' |' ) = 7 a H/'
4|H)' 2 52 (3H, ś,4 c{Hr cH', 2 r 7 GH, 5, 3 cll]). Elc
nenta]analysń lor caHDNr: ..lolitcd] c _ 32.49'
J,6.Dimethyl4 (a'meulylphenyl) I phrnyl lH py
razolo13, ,I tlquinolinc
PAQ5
Yeuow ĆrYstals, 3l x"ł,I'= 197_]93'c i (cycloh*
jH
xano) =43Sa nm
NMR GOO MHz. CDC|.):6aO CH.
tl,1 = 3,7 Hz,zrH,6rH),3.n (1H, tt) = 3.7 Hz,3.H\,7.57
-
l1H, d, I - a.76 H.z, 7.H), 7 55 (zH, t, I = 3.a Hz, 3:H,
51H), 747 (1H, s,5,H), 7.10 (2H, d, J = 3 2r Hz, rrH,
5:H), 7.33 (2H' d' J = 3 23 rŁ' 2:H, ó|H)' 7 '27 (1H, ] =
', s,
7.4 Hz, 4|H)' 2'53 (3H' s, ł c6HfcH', 2.43 (]H'
ó.cHl), 2 ra
(3
3
'
'
cłH!N'calculatgd:c
6-BIom o-3'n cth
ylr
cH'' llcńental
analysis lol
(a' methylphenyl).1?hcny
hQl
I r
!
pynzolo13, 4r,lquinoli,rcYellow oy*ik,32'l',, P
'205 20ó't' 1kyclohc'
xaM) = 447 lm' IH N'IR (3oo MnZ, cDcI]): 3'.tó (2H, d,
HŻ,8_H),7's6
]= 3'7 H2, 2' H, 6|H), 3'0ł (1H,d' l=
(1H,
2'aHŻ,
3
H),
7'75
d,
9
5,
'.r
|1H,
] = 1, ]' = 2.o 1-1:l,
]' =
7-H),7 5.
Hz, 3 -rt,
] =3 0llz'3'H,51H),7'4aęH,d,]=B1
rt),73r
5
cFI,d,J =3.1]l:2,2-H,6rH),723
Qll,l'
Thc'atjo of PAQ/PVKwBmainbincd żb.ur] j00(rhil
proportion was round *poimenbuy io 8i!c the sbnE
si enision in tlt. LED studure). lI ihc ncł *cP, thc
soluiion was deP6ikd by sph.ł*iĘ onto thc slaŚ
slbsbatePatńlly.oaEd frrh a r00 nm lóyrr of indlhhn oride (lTo) Thc avcrag. thickn*Ś Óf the orgatri.
liyer was mcasul€i to bc aboli 50 ną Flnall]ra r0 nń
r0'Pi)Jnd rhewhoh wasnpped Włh i L00nm i]u'
ni'rum Piottliv. layei The Óv.ra
oH, i'J = 7.4Hz,11H),2'33 (3l'I, s, !c6HłcH'' r.13
(3H, s,3.cHt Elcmcntal amlysis for caH sBrNr: cal.u.
ó lvlethoxy 3 h.thy1_1'(4hcihy1Phc.vl)_l-Phcnvl
rH-Pvnzo1o13' ł'lquirclinc _ PAQ3
]c ow.ryłils']0 . ł}, =al_rr2< rk!.loh!
a3j nń 'H NMn(]00\4Hz,cDcLJ 340(rH,
n,1 = 3'7 \1.,1', H,6', H),3 ll (1H, t, ) = s'2lŁ' $-HJ,7 '54
s
re)=
s.2Hz,l', =
ll,
x'
H,
1'
H,
ś.H),7'26
|1H,Ż'
(1H'
(lH,5,
7.4
rŁ'
41H),6.9a
| =2311?,5 |1),373
=
(3H' ',l
s, ó_ocHn,2'52 (3H, s' ,I.c6HłcHtr), 2 l a Gll,5,
].cHł' Eleh.nlal analvsis for c"lHINro cil.uliicd:
1211,t,)=7e7Hz,3
Ż3 z, 7 H)'7 36 7
11,5', H),7.nx (1H, d,t =
77
}Mł}yl +(a'ńethylPhenyl)
lH pyrazol.l3,+tlqlinohe
ó
phenov ] phen),l.
PAQ 2
= ej tu, sts),
(3ll, , Hi'oń),
7 07 oH,l,J = 7.3 Hz, ł-_H iI6.oPh)'ó97(2H'd,] -35
Hz, HN- ó.97 (2H, l' 2''|tI and 6- H i| oPl')' 2 4s
,r,I
= s.0
Hz,2'H, 6',8),
B20 OH, r, )
716 76r oH' ł' Hiijh)' 724_7
(3H, s'
.1
c6HJ
'
cH',
33
2'r7 (3H, s, 3
cHł''j El.nental
Br 6r,H 525,
folnd: C
6.chlorc'3.meih]'l.ł(4|m.lhy1phcn],l)-]-Phenyl1r'_
Frrlazorol3, 4,nquinorinc - P a6
Ycrrow nccdles, 30 ,/ , ,, f. = 20r-203 ,(]. I (._!dohe:anc) = 446 M] rH NMR Goo rvrHz
I = 8.7 Hz,2.H, 6' H), 3.12 nH, n, I = 9 0 Hz, P.H),7.63
(lH' s, J'= 2'3 Hz, 5 H)' 7'ó4 (]H,lt,l=9'0,l = 2.3 H1,
7'Hl,7'55 (2H, l,] = 3.a Lb,3' ll,5|H), 7'ło (2l'l' tl, J = 3'r
aMlyŚhktrcl HaNlo]calculatcd:c
N
9 52;
Hz,3 H,s rr),73r Oti,,J-I-sI Hz,2 H.6rH\.7rg
0H,l,l= 7ł Llz,41ll)' 2 G' 3H, 'l.c6Hr'cHł' 2'r,I G,
3r, 3 CHr) Elcmcntil in.lysjs
'3
for
lihd:C-75.09,H-17tN r095;tou|d,c
75.24
Multilayor eledloluńures.enc. diodcs wcrc ob-
loccdur.lr2l Thcy
w.r. pr+ared by $ djsolution ol rhc mabix polymer
(FvK) and L\Q! dsivJhvc in łchahydloluran (THF)'
The absorptiÓn sPeda wgc rc.od
fuhn sohtion using a shimidzu Uv-vls210i słnnin8
sPtbÓphotom.tł in llre nĘe 30
ńĆastefr.nś woc Pcrlonned LBin8 standłtl ] cm
Paih lcrylh qu tz cuvet.IÓr absorPtion sP..rńmdry
PL rd EL spe.ta wł. re.olded by neans ofxn oiel
ln*asPec II ńonochloń'tor/djodc JEiy dctcdor
QuaniumelfiĆien.yof Photolumjncfcn.ceL)wrse{i.
ńabd using a Hamanabu ]337Photodiode ind Kejth'
ley 437 P!.oimmd€r wilh qlininesulPhar. isshndald
rcfercn.c marerial. EL intrNiri$ r!
r0v usins no/PvK + PAQ/cr/Al c.ll
AbsorPtion and ?L spe.fu of th. PAQ doivatives
shown in Fig. 2. Al$orsh th. us
łc
drdnl allolv to di$insri\h dneiry bcnvecn pL and
phosphol*eń.ci lhślaśonc ( cvcl signific t) hłd lo
b. ĆhłałeliŻcdby lifPtin. sho e
ond shapcs of ib!Órptioń łnd PL sPsEa aft vrly sińi
la! fol ill invesli8afud nfiPouńds Ml!ńa of th.
'b'
sorpiion spe.ta viry f!Óń 390 ńń (PAQ6) b all m
(PAQ3)' Maii''a ol thc Photoluminś(ncc sPRba łrc
shilled iowards thc lon€el
wavelenElhs by .tr'
ó0
70
Thereordcdp.iksolELniximamver,I54 467nm
wavĆleĘrh nng. Ge Fi8 3)' EL m
e* walelcngrh is observed for PAQ5
POLIMERY 2004,
166
(PAQ3) and phenytoxy (PAQ2) side
Broups. It means
that electron-donating substiiuents COC6H5, -OCHJ en
hanc€ ELstren8th.ln case oI PAQ bealin8 an e]ectron-acceptor (Cl, Br), EL efficiency was generally poor (see
t0
0.8
49, nr 3
0.8
Table 1).
€01
2
0.4
a2
{
0,2
a b l e 1' Absorption PhotolumineŚc.Ąće (Pl) and €lectrolumi
nescen.e (Er) ńaxima and PAQS quanfum effiĆiencies (9P ańd a.l
T
Qualfuń .fficicncy,
PL
1.0
l0
PAQ]
PAQ2
PAQ3
.0.8
0.8
i06
l)'ż7
0,09
157
0.65
0.r9
457
PAQ.I
PAQ5
0.83
396
465
(]..58
PAQ6
455
454
391
459
0.008
0,02
481
0.009
FiSure 4 (elecboluminescence
curent LED'S characteristics) shows that EL values -of PAQ3 or PAQ4 are
rather high.
360 400 .l-40 480 520 560
Wavelcngth. nn
a d photol minescence QL)
PAQ:|-PAQ3, (b) PAQ4 PAQ6
Fig. 2. Absorptian
ptes: (a)
467
4t1
483
4ó2
456
405
ri
bo 4
0.0
40r
1,
of
600
PAQ sam-
PAQ4.
.{ d
r00
l0
PAQ3
PAQ2
.il
,?
0l
o.0l
.j
0.4
0.1
l0
'nA
FiS. 4. Depenllence of electrcluninescence (EL) an the cl.Lrrent
0.2
of
00
I
Crr.nr
]50
400 450 500 550
Wavclength,
F'ig. 3. Electraluninescence
Iayet of ?atiaus PAQ in
nn
ńo0
(EL) spectn of LEDł loith actire
PvK naiirl
lateral group. On the other hand, EL maximum ofPAQ1
(Br as lateral group) is shifted to longer wavelengths,
relatively to its PL spech.um, only by 13 nm. Comparing
the guanlum elńciencies of Pl łnd tL or ]-AQl ana
PAQ6 one can see the negative influence of heavy atom
(Br, Cl) presence. The most efficient PL followed by best
recorded EL was found in PAQ containing metoxy
PAQ
based
LEDł
Analysis of the cource ofa dependence EL - f (, Vcurrent density) sho\^r's tlrat for PAQI, PAQs and PAQó
an el€Ćtroluminescence can be described as fol]owj EL/n,
whe|€ n is close to 2 [1]' This phenomenon can be ex_
plained on the basis of a model of injection conrrolled
electroluminescence (ICEL) 1131. In rhe case of charactedstics other types of PAQ it is difficuli ro do a simple
interpretation.
So, from the rcsults prcsented, tesrifing to depcndence of pyrazoloquinolines eleĆtroluminescence P.operties on the substituent, it is clear that both the position of electroluminescence maxima as well as quantum
ofefficienry yield can be controlled.
,1crNoWŁEDGMENTS
Th;sŃ*M
paay
slpplłtl Ę Palish
|d s.jln it'h RMfth łKBN), gldĄl Na
l'
2'
4
shle
cńńłlł
TwE a97 25
t<ali.oMki l| / !,ryś'D
P'yJ' 199ą 32' RDs'
'4Pl'
schod M': c' R',Ąfid' s.j !ffiś9'
2000i 1,3€1'
'y
Ar 1. Sti. Prtt s. rr' ma],\ 425.
Micha.lis A., Li.bĘg J.: ńtr'' clol' r911,1, 335.
Niziol J., Danel A , Gondek E'' Amatys !', sańeh J :
Mdmor. symp., ro be Published
'l{\'1', ą1|chln' hklł
no\B'1207.
7'
Bqdal D', siępień
I',
sanch
J',
c
3' BB.k A'] LnĘ,4itr' Ć'ł' 1965,63! rrr.
e. Hemt 1., Miiuer r., cm.ne Mr I !ni.. c,,.,.
P: Palk)h
12'
tr
J.
ctm.mqj,71,1141.
s ch l, Błb B, Niziol
.hfuki l: s!'l''. Md ]99€'
K.ril1fulit: fiuthphob
s, chrząsz.z
R', Pieli
]23'
and LjShrDnvrD Mul-
rialsan'lAPP]Euon{,(Edś'r'Parf,AAmmqó
M' vl W| ?ą K]uW Aodńr PuHBlr6 2mo'