Ti¾ c m ° i¾  Acc ½ Mf° ¾ci½ v ¾i° f f P bi¾ Wk f f½½ f i° fi°f fm i° RSC A vŦ, 2016, 6, 9247 DOI: 10Ŧ1039$c5f21959k New solution-processable carbazole derivatives as deep blue emitters for Organic Light-Emitting Diodes f f b c Mff R i–, Gi  B b°i ° , W   Cfmbff , Vy–i°f¾ Jf°kf ¾kf¾, Vyf f¾ G f i¾, b, f *f Emii Pfmf ¾, E – °if Mfí° z-&   f° D ¾ V f¾c Tw ° w cm½ ° ¾ bf¾ °  cfbfz °i¾ c°° c by i½ b° ¾ f¾ π-¾½fc ¾ fv b ° v ½ f¾ ½ b mi ¾ f –f°ic i–- mii°– i ¾ (OLED¾)Ŧ T i ½icf f°  cc micf ½½ i ¾ w  xfmi° f°  cf– cfi  f°¾½ ½½ i ¾ w  i°v ¾i–f by m f°¾ f  x –f½ic im -f-fi– (XTO&)  c°iq Ŧ T ½ ½f i ¾ m°¾f  f f¾ibiiy f  ° w m c  ¾ f¾ ff civ mi ¾ i°  ½ b  –i° yi  i°– vic ¾ wi w  °-° vf– ¾Ŧ Introduction O–f°ic i–- mii°– i ¾ (OLED¾) fv b ° ¾ i x °¾iv y   i ½mi¾i°– f½½icfi°¾ i° ff-½f°  i¾½fy¾ f° ¾i -¾f i–i°–Ŧ Hw v , f   im½v m ° f ½w  ffici °cy, c  ½ iy f° °–  ½ fi°f if im ¾ f ¾i  q i  ½ c ffici ° i° ¾if vic ¾Ŧ T v ½m ° f OLED¾ f mi i°  b  –i° ( fi° by  Cmmi¾¾i° I° °fi°f ’Ecfif– cmficiy y c i°f (CIEy) vf  ¾¾ f° 0Ŧ1) fv ffc i° °¾iv  ¾ fc, ¾i°c  ¾ mf if¾ cf° b f½½i i° cmbi°fi°  – ° f°  c  mi ¾ i° wi OLED¾ f° f -c  i¾½fy¾Ŧ W  f¾ – ° f°  mi ¾ fv  fc f m ¾ cc ¾¾f  v ½m °,  ffbicfi° f i– ½w - ffici °cy f° bi– b OLED¾ i¾ cm½ x   i°i°¾ic f– bf° –f½¾ f  –f°ic mf if¾, wic iffic   i°j ci° f cf– ¾ i°  mi ¾, f°  w  ¾ °¾iiviy f   mf° y i° i¾ ½f f   cmf–° ic ¾½ c m, wic c f¾ ¾  fficfcyŦ I° f ii°, b OLED¾ f m ½°  –f fi° ¾wi°– ½ °–- m ¾fbiiy f° ¾  1 if im ¾Ŧ N v   ¾¾, ¾ v f ffici ° ½-b OLED¾ 2 fv b °  ½ wi   ¾ f ¾- ½f° ¾y¾ m¾Ŧ Cfbfz bf¾ cm½ ° ¾ fv b °  ½ f¾ – 3 cf° i f ¾ f  f°¾½ mf if¾Ŧ I° f ii°,   fiv y w fk π- °fi°– fbiiy f  cfbfz mi y 4 mfk ¾ f  m ¾ ifb cf° i f ¾ f ½-b mi ¾Ŧ T  f ,  ¾i–° f ° w cfbfz bf¾ y ¾ f c  ½ ¾ ° b b f  ¾c ° ½½ i ¾ f°  f°¾½ cffc i¾ic¾ i¾ f° ffciv cf °– Ŧ H  i° w ½ ¾ °  ¾y° ¾i¾ f° ½y¾icf ½½ i ¾ f w ° w y ¾, wic i°c½f  cfbfz °i¾ i°  i ¾i–° (Sc m 1)Ŧ W  f¾  c °f cfbfz °i f¾ b ° mfi°fi° wi ° ¾ b¾i i° i°  °i– ° fm  ffv   c°ic cfizfi°,  w x °f cfbfz °i¾ c°° c   3 f° 6 ½¾ii°¾ f  c °f c fv b ° ¾ b¾i  by w iff  ° – ½¾  i° c ¾ ic i° f°c i°    –  i–  q f° m yi  ¾Ŧ T cfbfz i½ bf¾ ¾ b¾i i° f¾ b ° ¾  c  ½m  mi° ¾c °c i°  b z° f  vi¾ib ¾½ c mŦ &  m , cfbfz ivfiv ¾ f ¾ b i° mf°y ¾v °¾, v cmi°–  i°¾ biiy f ¾mf m c  ¾ f° ½ °i°–     c°¾ ci° f OLED¾ by ¾ i° ½c ¾¾i°–Ŧ Results and discussion Synthesis and characterization a. 2 Grup de Materials Orgànics, Institut de Nanociència i Nanotecnologia (IN UB), Departament de Química Orgànica, Universitat de Barcelona, Martí i Franquès 1, E-08028, Barcelona, Spain. E-mail: dvelasco@ub.edu; Fax: +34 93 339 78 78; Tel: +34 93 403 92 60 b. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avda. Països Catalans, 16, E-43007, Tarragona, Spain. c. Department of Solid State Electronics, Vilnius University, Sauletekio al. 9, Vilnius, LT-10222, Lithuania. d. Department of Organic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, Kaunas, LT-50254, Lithuania. e. Catalan Institution for Research and Advance Studies (ICREA), Avda. Lluis Companys 23, E-08010 Barcelona, Spain. f. Fundació Eurecat. Av. d’Ernest Lluch 36, Parc Científic i de la Innovació TecnoCampus, E-08302, Mataró, Barcelona, Spain. & &° ¾  f°–    f° $ f ¾ ¾  f½½ f   Ŧ E c°ic S ½½ m °fy I°fmfi° (ESI) fvfifb : 1H NMR, 13C NMR f° mf¾¾ ¾½ cf, Cycic vfmm–fm¾, XTO& cffc i¾ic¾, fv f– vf ¾ f OLED vic ¾ f° i–if ½ic  f f° OLED vic Ŧ S DOI: 10Ŧ1039$x0xx00000x Tw ° w b f  ¾c ° cfbfz -bf¾ y ¾ w  ¾i–° f° ¾y° ¾iz , f¾ ¾w° i° Sc m 1Ŧ S°–f¾if c ½i°– 5 6  fci° f 3,6- i y°y-9H-cfbfz wi 1 f° 2 i°  ½ ¾ °c f i yfmi° (TEA) °  P (PP3)2C2 cffy¾i¾ –fv fi°f ivfiv ¾ 3,6-bi¾[2-(9-(2- y xy)-9H-cfbfz-3y) y°y]-9H-cfbfz (3a) f° 3,6-bi¾[2-(9-(3,5- i-tert(3b), b y½ °y)-9H-cfbfz-3-y) y°y]-9H-cfbfz 7  ¾½ civ yŦ P vi ¾y, cm½ ° ¾ 1 f° 2 w  ½ ½f 8 fm 3-i -9H-cfbfz (MIC) wi 2- y xy bmi i°  ½ ¾ °c f KOH f° 1-bm-3,5- i-tert-b yb °z ° ,  ¾½ civ yŦ I°    –  c ½i°– ½ c 3b i° i–  yi  , f ¾ c° ¾y° ic   wf¾ i°v ¾i–f fm 3,6- ii -9H8 cfbfz (DIC)Ŧ & f ½ ½¾ 9-(3,5- i-tert-b y½ °y)- H H N N I Pd(PPh3)2Cl2 N H CuI, TEA THF, r.t. N N H 1 3a H H N N I Pd(PPh3)2Cl2 N H CuI, TEA THF, r.t. N N H 2 3b I I H Si(CH3)3 I N H DIC N Si(CH3)3 N Pd(PPh3)2Cl2 CuI, TEA THF, r.t. K2CO3 N Pd(PPh3)2Cl2 CuI, TEA THF, r.t. MeOH, r.t. 2 5 4 Scheme 1 Sy° ic   ¾ wf ¾ 3a f° 3bŦ 3-[2-(im y¾iy) y°y)]-9H-cfbfz (4) f° 9-(3,5- itert-b y½ °y)-3- y°y-9H-cfbfz (5) w  ½ ½f fm cm½ ° 2Ŧ T ¾ c°   fff f ¾i– i°c f¾ f  yi  fm 15  24 %Ŧ T c micf ¾ c  f f ¾y° ¾iz cm½ ° ¾ wf¾ 1 13 c°fim by ¾½ c¾c½y  c°iq ¾ ( H NMR f° C NMR) f° mf¾¾ ¾½ cfŦ Photophysical properties M c  ¾ 3a f° 3b f ¾ b i° cmm° –f°ic ¾v °¾ ¾ c f¾ cb °z ° , icm f°   fy f f°Ŧ T ½½y¾icf ½½ i ¾ f y ¾ 3a f° 3b i° ¾ i° f° i° ¾i ¾f f ¾ mmfiz i° Tfb 1Ŧ &  ¾c °c m f¾  m °¾ i° icm f° ¾ i°, ff  xcifi° f 300 °m, ¾w mfxim m f  ¾c ° ½ fk¾ c ° f 371 f° 392, f° f 369 f° 390 °m, f 3a f° 3b,  ¾½ civ yŦ T mi¾¾i° i° ¾i ¾f ¾fm½ ¾ ff  ½ xcifi°  ° ¾ f ¾i°– ½ fk i° b cf¾ ¾ cf f 410 f° 398 °m,  ¾½ civ y (&i–Ŧ 1)Ŧ T bfcmic ¾if b¾ v i°  ¾i ¾f mi¾¾i°, cm½f   m f¾  m °¾ i° ¾ i°, i¾ m vi ° °  3a m c    w  ¾ ic i° f°c , i° cm½fi¾°  cm½ ° 3b wi  3,5 i-tert-b y½ °y – ½, fwi°– b   vf°  Wff¾ i° fci°¾ b w ° ° i–b i°– m c  ¾Ŧ T q f° m yi  f  N-fy ¾ b¾i  3b ¾i ¾f i°-fim¾ ½¾ fm 0Ŧ31 i° ¾ i°  0Ŧ11 i°  ¾i ¾f , wi  Nfkyf f°f– 3a mfi°fi° ¾ b¾f°ify °cf°– i¾ f  ¾c °c ffici °cyŦ T  f ,  i° ci° f  2 y xy ¾ b¾i i° °  cfbfz °i¾ f¾ Table 1 O½icf f°  cc micf ½½ i ¾ f cm½ ° ¾ 3a f° 3bŦ compd. 3a 3b a λabs, max (nm) a 305, 325, 349 305, 324, 349 λem, max (nm) a 371, 392 369, 390 Φa 0Ŧ39 0Ŧ31 λem, max (nm) b 410 398 Φb 0Ŧ31 0Ŧ11 CIE b (0Ŧ17, 0Ŧ07) (0Ŧ18, 0Ŧ11) Egap (eV) c 3Ŧ32 3Ŧ33 Eonsetox (V) d 0Ŧ93 0Ŧ99 IP (eV) e 5Ŧ89 5Ŧ95 EA (eV) 2Ŧ57 2Ŧ62 M f¾  i° CH2C2 f 10 µMŦ Q f° m yi  m f¾  m °¾ (Φ) w  ° ff  xcifi° f 300 °m ¾i°– POPOP f¾  ¾f° f  f  °c (1,4-bi¾(5-½ °y-2-xfzy)b °z ° )Ŧ b M f¾  i° i° fim¾ ° q fz ¾ b¾f ¾Ŧ c O½icf –f½ ° –yŦ O°¾  xi fi° ½ °if  mi° fm cycic vfmm yŦ IP = E°¾ x - E0(&c$&c+) + 5Ŧ39Ŧ Fig. 1 P mi° ¾c °c ¾½ cf f cm½ ° ¾ 3a f° 3b f) i° icm f° f f c°c °fi° f 10 μM f° b) i°  ¾i ¾f Ŧ m°¾f  b m ffici °  fvi  q °ci°– f  f  ¾c °c , f°  ¾ ic i° f°c i° c by  3,5- i-tert-b y½ °y – ½Ŧ I i¾ w  fk i° fcc ° f   cfbfz °i¾ i° m c  ¾ 3a f° 3b f i°k by f i½ b° Ŧ W °  i½ b° i¾ ¾ f¾ f π¾½fc   Sk ¾ Sif i¾  c i° cm½fi¾°    b 9 b° f°f– k ½i°–  f  ¾c °c mi¾¾i° wfv  °– i°  b z° Ŧ I i¾ i°  ¾i°–  i–i– f b cm½ ° ¾ ½ ¾ ° f CIE y c i°f i°  f°– f  ½ b  –i° mi¾¾i° (CIE y c i°f w  f° 0Ŧ1)Ŧ I°    i°c f¾ ffici °cy i° OLED vic ¾ i i¾ f – ¾f –y  ¾i–°  mi° ¾c ° y ¾, ° °y wi i– q f° m yi  ¾ i°  ¾i ¾f f  ¾  c wfv  °–¾ b  f¾ wi i– cf– cfi  mbiii ¾  ffv   w  c mi° ¾c °c ½c ¾¾Ŧ Electrochemical properties E cc micf ½½ i ¾ f cm½ ° ¾ 3a f° 3b w  f°fy¾ Ŧ Cycic vfmm y (CV) f b cm½ ° ¾ w  ½ fm i° icm f° c°fi°i°– 0Ŧ1 M TBAP f¾  ¾ ½½i°–  cy Ŧ B cm½ ° ¾ ¾w ° i v ¾ib xi fi° ½c ¾¾ by cycic vfmm y (&i–Ŧ S17& i°  ESI), b i°– b ¾fb    ci° ½c ¾¾Ŧ Tfb 1 c c¾   cc micf cffc i¾ic¾Ŧ Hi– i°izfi° ½ °if (IP) vf ¾ (~5Ŧ9 V), ¾imf fm xi fi° °¾  ½ °if¾ by cycic vfmm y, f° i– ½icf –f½ ° –y vf ¾ (~3Ŧ3 V), ¾imf i° cmbi°fi° wi UV-vi¾ib ¾½ cf, w  bfi° f cm½ ° 3a f° 3b, wic f i° icfiv f ½ °if  c° ci° ½½ i ¾Ŧ T ¾ b¾i i° f  °i– ° fm¾ f  cfbfz mi i ¾ f¾ f ¾i– i°f °c °  i°izfi° ½ °if vf ¾, b i°–  i°izfi° ½ °if f  N-fy ivfiv 3b ¾i–y i– Ŧ T °f  f  π-¾½fc  b w ° w cfbfz °i¾ 9 i°f °c ¾   c° fffi°iy (EA) vf ¾Ŧ Lw  EA vf ¾ w  bfi° f bicfbfz ivfiv ¾ b° by w c°¾ c iv i½ b° ¾, i°¾ f f by °y °  b b°  ° i½ b° Ŧ Cm½ ° ¾ 3a f° 3b, wic c°¾i¾ °  cfbfz °i¾ wi f i½ b° f¾ f π-¾½fc  i° cff b w °  m, ½ ¾ ° w EA vf ¾ wic ½ °ify ffciif ¾  c° i°j ci° i°  fciv fy Ŧ Charge transport properties I°izfi° ½ °if (IP), wic cffc iz ¾   c°   f¾i°– wk °  i mi°fi°, wf¾ f¾  mi° i°  ¾i ¾f f b 3a f° 3b cm½ ° ¾ by  ½ mi¾¾i° i° fi m  Ŧ P mi¾¾i° ¾½ cf f  fm½ ¾ fim¾ f b cm½ ° ¾ i° fi f ¾w° i° &i–Ŧ 2fŦ IP vf ¾ f cm½ ° ¾ 3a f° 3b f 5Ŧ33 f° 5Ŧ44 V,  ¾½ civ y, c¾  f f i° i m i° xi (4Ŧ8 V)Ŧ T °f  f  N-¾ b¾i °¾ f  cfbfz c f¾ °y f ¾i– i°f °c °  i°izfi° ½ °if vf ¾Ŧ Ti¾ b¾ vfi° i¾ i° f– m ° wi ½ vi ¾  ½¾ w  i wf¾ f ° f  m ificfi° f  ¾ b¾i i° ½f °¾ f  cfbfz mi y ½fcicfy  ¾ ° fff c  i°izfi° 10 ° –y vf ¾Ŧ I ¾  b fk ° i° fcc ° f fm   cc micf ½½ i ¾,  IP vf ¾ f cm½ ° ¾ 3a f° 3b (Tfb 1) w   mi° i° ¾ i°, w  f¾ i°  ½ mi¾¾i° i° fi  c°iq  IP i¾  f   ¾i i°fim¾Ŧ Ti¾ ¾i–y iff  °c i° IP vf ¾ bfi° fm  11 w iff  °  c°iq ¾ f¾ b ° ½ vi ¾y  ½ Ŧ Fig. 2 f) P mi¾¾i° ¾½ cf f  fm½ ¾ fim¾ f cm½ ° ¾ 3a f° 3b m f¾  i° fi f 25°CŦ b) XTO& f°¾i °¾ f cm½ ° 3a m f¾  f 25°C. I°¾  ¾w¾ ° f°¾i ° c v i° i° f ½Ŧ Table 2 Dff f b ¾ OLED vic ¾ bf¾ ° cm½ ° 3a. device Fig. 3 A&M imf– f f ¾ i°-½c ¾¾ 3a bf¾ i°-fim fm w iff  ° ½i°¾ f vi w (5 × 5 μm2)Ŧ &  ¾imfi° f  f°¾½ ½½ i ¾, fm½ ¾ fy ¾ f  ¾y° ¾iz mf if¾ w  ½ ½f f° ¾ bj c   X –f½ic Tim -f-&i– (XTO&) m f¾  m °¾Ŧ R ½ ¾ °fiv XTO& f°¾i °¾ f  f°¾½ f cm½ ° 3a f i¾½fy i° &i–  3f, ¾wi°– f i¾½ ¾iv ½f °Ŧ T f m½¾  ¾imf   mbiiy f cm½ ° 3b w  °¾ cc ¾¾f ,   m c m i¾½ ¾iv mbiiy  –i¾  f f cm½ ° Ŧ T  -f°¾i im ¾ (t) f 3a w  ¾fbi¾ fm i° ¾ ci° ½i°¾ f w f¾ym½ ¾ fm   b –fimic ½¾ (&i–Ŧ 2b)Ŧ T ½ ° °cy f  if mbiii ¾ °  ¾q f  f   cic fi  f cm½ ° 3a i¾  ½ ¾ ° i° &i–Ŧ S18& i°  ESIŦ Cm½ ° -7 3a ¾w f z  fi   if mbiiy (µ0) f 2Ŧ6 × 10 2 cm $V¾ f° f fi  ½ ° °c ½ffm   (α) f ∼0Ŧ0087 1$2 (cm$V) Ŧ Cm½ ° 3a ¾w f  cf– mbiiy f 2Ŧ8 -4 2 5 × 10 cm $V¾ f f  cic fi  f 6Ŧ4 x 10 V$cm, wic i¾  fiv y i– f° ¾ f  f ½fcicf f½½icfi°¾Ŧ Organic Light-Emitting Diodes T ½icf f°  cc micf ½½ i ¾ f cm½ ° 3a,  i– q f° m yi  i°  ¾i ¾f , –   wi  ¾ ifb b CIE c i°f ¾ f°  mbiiy vf ¾ c°f  ° 3a  ¾ – cffc i¾ic¾ f f° ffici °  mi° ¾c ° y i°  ½ b mi¾¾i° f°– Ŧ O°    f° , fim m½–y f  mii°– fy  ¾°–y i°f °c ¾  ½ fmf°c f  –f°ic vic ¾Ŧ Tf½½i°– m Amic &c Mic¾c½y (A&M) wf¾ ½ fm i°    cffc iz  m½–y f  i°-fim bf¾ ° 1 2 3 4 5 6 7 solvent a CB CB CB CB CB DCM TH& d (nm) 25 30 40 50 55 25 25 b Vt (V) c 2Ŧ80 2Ŧ68 2Ŧ88 3Ŧ23 3Ŧ62 2Ŧ61 2Ŧ62 Lmax (cd/m2) d 35Ŧ59 37Ŧ52 40Ŧ98 39Ŧ46 33Ŧ49 24Ŧ75 26Ŧ47 ηc (cd/A) e 0Ŧ08 0Ŧ09 0Ŧ09 0Ŧ17 0Ŧ05 0Ŧ03 0Ŧ03 Av f– vf ¾ f  ½ i° Tfb S1& i°  ESIŦ a Sv ° ¾ f ½ ½fi°–  3a bf¾ fy  by ¾½i°-cfi°– (CB: cb °z ° , DCM: icm f° , TH&:  fy f f°)Ŧ b Tick° ¾¾ f  3a bf¾ fy  m f¾  wi f ½fim  Ŧ c T °-° vf– fi° f¾ vf– c ¾½° i°–  f  mi°f°c f 0Ŧ1 c $m2Ŧ Mfxim m  mi°f°c Ŧ Mfxim m c  ° ffici °cyŦ cm½ ° 3a (&i–Ŧ 3)Ŧ 25 °m ick fim¾ w  ½ ½f by ¾½i° cf¾i°– f f cb °z ° ¾ i° f cm½ ° 3a ° f PEDOT:PSS  f ITO ¾ b¾f Ŧ A&M imf– ¾ ¾w m– °  ¾ f° c°i°  ¾ i°-fim¾ f cm½ ° 3a ½ ½f by ¾ i° ½c ¾¾i°– wi f -m f°-¾q f (m¾)  –° ¾¾ f ∼1Ŧ46 °m, ¾wi°– f½½½if m½–y fy  cffc i¾ic¾Ŧ C°¾ q °y,  m c  3a f¾ b °  ¾ f¾ mi¾¾iv fy  i° °°- ½ ¾i°– -fy  i– mii°– i ¾Ŧ T   ½ ¾ ° OLED c°fi– fi° c°¾i¾ ° ITO$PEDOT:PSS (25 °m)$3a (25-55 °m)$TPBi (10 °m)$Li& (1 °m)$A (100 °m) (&i–Ŧ 4f)Ŧ I°    ½imiz  ½ fmf°c f  vic ¾ iff  ° ick° ¾¾ ¾, fm 25  55 °m, f  3a fy  w  ½ ½f fm cb °z ° ¾ i° by ¾½i° cfi°–Ŧ T ½ fmf°c cffc i¾ic¾ f  iff  ° vic ¾ f ¾ mmfiz i° &i–Ŧ 4b f° 4c f° Tfb 2Ŧ D ½¾ii° f  mi¾¾iv fy  f cm½ ° 3a wf¾ f¾  ¾ fm iff  ° ¾v ° ¾ i°¾, ¾ c f¾ icm f° f°  fy f f°Ŧ A  vic ¾ ½ ¾ ° cm½ iiv  °-° vf– ¾ b w ° 2Ŧ6 f° 3Ŧ6 V i° icfi°– ¾mf i°j ci° bfi ¾ fm  f°¾½i°– fy ¾ i°  vic Ŧ T  mi°f°c i°c f¾ ¾ ½° vf– f½½icfi°,  fci°–  mfxim m vf ¾ b w 5 VŦ T mfxim m  mi°f°c vf ¾ f ½ ° ° °  Fig. 4 f) E° – ic ¾c m f  iff  ° cm½° °¾ f  vic ¾ c  ¾ i° i¾ ¾ yŦ T f¾ i° i° 3a cm½° ° i° icf ¾  i°izfi° ½ °if bfi° fm  ½- mi¾¾i° i° fi  c°iq Ŧ Ti¾ vf i¾ i¾½fy i° ½f ° ¾ ¾Ŧ b) C  ° °¾iy-vf– f° c)  mi°f°c -vf– cffc i¾ic¾ f  vic ¾ ¾ mmfiz i° Tfb 2Ŧ ick° ¾¾ f  fciv fy ,  fci°–  ½im m fi b w °  mi°f°c f° c  ° ffici °cy f 50 °mŦ &   i°c f¾ f  ick° ¾¾  f ¾  f c f¾ f  mfxim m  mi°f°c f° ffici °cy –   wi f° i°c f¾ f   °° vf– , ½i°i°–  –wi°– °bff°c f  cf– f°¾½ i°  vic Ŧ O°    f° ,  vic ¾ ½ ½f fm DCM f° TH& ¾ i°¾ ¾w ½  ½ fmf°c ¾ ¾ –– ¾i°–  i°f °c f  ¾v ° °  fi°f m½–y f  fciv fy Ŧ Conclusions Ticfbfz ¾ 3a f° 3b ¾w  ¾ – ½ b mi¾¾i° i°  ¾i ¾f , f¾ f  ¾  f i°ki°–   cfbfz °i¾ by f i½ b° f¾ f π-¾½fc Ŧ I° f ii°, fkyfi° f  °i– ° ½¾ii°¾ f  f f cfbfz °i¾ wi 2 y xy cfi°¾ f°¾f ¾  q f° m yi   mi° i° ¾ i°  f i°  ¾i ¾f wi  ¾i–°ificf°  ci°Ŧ S i° ½c ¾¾ °°- ½ OLED vic ¾ fm cm½ ° 3a m°¾f ¾ i¾ ½ °if f¾ f b ½ mi  i° °°2 ½ vic ¾,  fci°–  mi°f°c ¾ f ½  40 c $m f° c  ° ffici °cy f 0Ŧ2 c $AŦ Experimental Materials A c micf¾ w  f cmm cif –f f° ¾ f¾  c iv Ŧ A ¾v °¾ w  i f° –f¾¾ by ¾f° f m  ¾Ŧ T fy f f° wf¾ i¾i fm ¾ i m$b °z½ °° Ŧ T ¾fi°– mf if¾ 3-i -9H-cfbfz (MIC) f° 3,6 ii -9H-cfbfz (DIC) w  bfi° fcc i°–   8 ½c  ¾ ¾cib i°  i f  Ŧ 3,6- i y°y-9Hcfbfz wf¾ ¾y° ¾iz fm 3,6- ii -9H-cfbfz 6 fcc i°–   ½ ½c  ¾Ŧ Synthesis of 9-(2-ethylhexyl)-3-iodo-9H-carbazole (1) 1Ŧ20 – (4Ŧ09 mm) f 3-i -9H-cfbfz i¾¾v i° 10 m f DM&, 2Ŧ37 – (12Ŧ27 mm, 2Ŧ18 mL) f 2- y xy bmi , 0Ŧ92 – (16Ŧ36 mm) f KOH f° 0Ŧ58 – (4Ŧ09 mm) f f°y  ¾ Nf2SO4 w  ¾i f m  m½ f  f 10 mi°Ŧ Af   mi°fi° f   fci°,   fci° mix  wf¾ i  wi wf  f°  ½ c wf¾ xfc wi y fc f Ŧ T –f°ic fy  wf¾ wf¾  –y wi wf  °i  fq  ¾ fy  wf¾ ° f, i v  f°y  ¾ M–SO4, fi  ff f°  ¾v ° wf¾ i¾i ff °   c ½ ¾¾  Ŧ T c wf¾ ½ ifi by ff¾ c m° cmf–f½y ¾i°–  xf° f¾   °Ŧ T yi  1 wf¾ 1Ŧ30 – (80%)Ŧ H NMR (400 MHz, d6-fc ° ) δ (½½m): 8Ŧ50 ( , J = 1Ŧ7 Hz, 1H), 8Ŧ18 ( , J = 7Ŧ8 Hz, 1H), 7Ŧ72 ( , J1 = 8Ŧ6 Hz, J2 = 1Ŧ7 Hz, 1H), 7Ŧ56 ( , J = 8Ŧ3 Hz, 1H), 7Ŧ51-7Ŧ47 (m, 1H), 7Ŧ43 ( , J = 8Ŧ6 Hz, 1H), 7Ŧ25-7Ŧ21 (m, 1H), 4Ŧ30 ( , J = 7Ŧ6 Hz, 2H), 2Ŧ14-2Ŧ07 (m, 1H), 1Ŧ46-1Ŧ17 (m, 8H), 0Ŧ91 (, J = 7Ŧ5 Hz, 3H), 0Ŧ81 (, J = 7Ŧ2 Hz, 3H)Ŧ Synthesis of 9-(3,5-di-tert-butylphenyl)-3-iodo-9H-carbazole (2) 4Ŧ50 – (15Ŧ35 mm) f 3-i -9H-cfbfz , 12Ŧ40 – (46Ŧ05 mm) f 1-bm-3,5- i-tert-b yb °z ° , 4Ŧ24 – (30Ŧ70 mm) f f°y  ¾ K2CO3 f° 0Ŧ13 – (1Ŧ99 mm) f C ½w  wf¾  f x i° 35 m f f°y  ¾ DM& °  °i– ° fm¾½  f 72 Ŧ Af ,   fci° mix  wf¾ fi   – C i f° i  wi wf Ŧ T ½ c wf¾ xfc wi y fc f f°  –f°ic fy  wf¾ wf¾  –y wi wf  °i  fq  ¾ fy  wf¾ ° fŦ T –f°ic xfc wf¾ i v  f°y  ¾ M–SO4, fi  ff f°  ¾v ° wf¾ i¾i ff °   c ½ ¾¾  Ŧ T  ¾i wf¾ ½ ifi by c m° cmf–f½y ¾i°–  xf° 1 f¾   °Ŧ T yi  wf¾ 1Ŧ51 – (21%)Ŧ H NMR (400 MHz, d6-fc ° ) δ (½½m): 8Ŧ59 ( , J = 1Ŧ7 Hz, 1H), 8Ŧ27 ( , J = 7Ŧ8 Hz, 1H), 7Ŧ71 ( , J = 8Ŧ6 Hz, J = 1Ŧ7 Hz, 1H), 7Ŧ67 (, J = 1Ŧ7 Hz, 1H), 7Ŧ50–7Ŧ45 (m, 3H), 7Ŧ41 ( , J = 8Ŧ2 Hz, 1H), 7Ŧ33–7Ŧ29 (m, 1H), 13 7Ŧ26 ( , J = 8Ŧ6 Hz, 1H), 1Ŧ42 (¾, 18H)Ŧ C NMR (100 MHz, d6fc ° ) δ (½½m): 153Ŧ8, 141Ŧ8, 141Ŧ0, 137Ŧ3, 135Ŧ1, 130Ŧ0, 127Ŧ8, 126Ŧ7, 122Ŧ8, 122Ŧ6, 121Ŧ8, 121Ŧ5, 121Ŧ2, 113Ŧ0, 110Ŧ8, 82Ŧ6, 35Ŧ8, 31Ŧ7Ŧ HRMS (ESI-MS) (m$z): cfc f C26H29IN (M + + H) 482Ŧ1339, f ° : 482Ŧ1348Ŧ Synthesis of 3,6-bis[2-(9-(2-ethylhexyl)-9H-carbazol-3-yl)ethynyl]9H-carbazole (3a) 1Ŧ19 – (2Ŧ94 mm) f 9-(2- y xy)-3-i -9H-cfbfz (1), 0Ŧ035 – (0Ŧ05 mm) f P (PP3)2C2 f° 0Ŧ025 – (0Ŧ13 mm) f C I w  i¾¾v i° 10 mL f f°y  ¾ TH& °  °i– ° fm¾½  Ŧ T °, 0Ŧ35 – (3Ŧ43 mm, 0Ŧ48 mL) f i yfmi° f° f ¾ i° f 3,6- i y°y-9H-cfbfz (0Ŧ21 –, 0Ŧ98 mm) i° TH& w  f f° ¾i f m  m½ f  f 10 mi°Ŧ Af   mi°fi° f   fci°, 3a wf¾ i¾f fcc i°–   ½c  ¾cib f 2, ¾i°– f mix  f  xf° f° y fc f (9:1 v$v) f¾   °Ŧ 1 T yi  wf¾ 0Ŧ23 – (31%)Ŧ H NMR (400 MHz, d6-fc ° ) δ (½½m): 10Ŧ74 (¾, 1H, NH), 8Ŧ46 (¾, 2H), 8Ŧ39 ( , J = 0Ŧ8 Hz, 2H), 8Ŧ25 ( , J = 7Ŧ9 Hz, 2H), 7Ŧ69-7Ŧ58 (m, 10H), 7Ŧ53–7Ŧ48 (m, 2H), 7Ŧ29–7Ŧ24 (m, 2H), 4Ŧ35 ( , J = 7Ŧ6 Hz, 4H), 2Ŧ18-2Ŧ10 (m, 2H), 1Ŧ50-1Ŧ19 (m, 16H), 0Ŧ94 (, J = 7Ŧ4 Hz, 6H), 0Ŧ83 (, J = 7Ŧ2 Hz, 13 6H)Ŧ C NMR (100 MHz, CDC3) δ (½½m): 141Ŧ4, 140Ŧ6, 139Ŧ3, 130Ŧ0, 129Ŧ3, 126Ŧ1, 124Ŧ1, 124Ŧ0, 123Ŧ3, 123Ŧ0, 122Ŧ6, 120Ŧ6, 119Ŧ4, 115Ŧ4, 113Ŧ8, 110Ŧ9, 109Ŧ3, 109Ŧ2, 89Ŧ3, 88Ŧ6, 47Ŧ7, 39Ŧ5, 31Ŧ2, 28Ŧ9, 24Ŧ6, 23Ŧ2, 14Ŧ2, 11Ŧ1Ŧ HRMS (ESI-MS) (m$z): cfc + f C56H56N3 (M + H) 770Ŧ4469, f ° : 770Ŧ4437Ŧ Synthesis of 3,6-bis[2-(9-(3,5-di-tert-butylphenyl)-9H-carbazol-3yl)ethynyl]-9H-carbazole (3b) Method A. 3b wf¾ ½ ½f f° i¾f fcc i°–   ½c  ¾cib f 3a, ¾i°– 0Ŧ11 – (0Ŧ51 mm) f 3,6 i y°y-9H-cfbfz , 0Ŧ74 – (1Ŧ53 mm) f 2, 0Ŧ018 – (0Ŧ026 mm) f P (PP3)2C2, 0Ŧ013 – (0Ŧ07 mm) f C I f° 0Ŧ18 – (1Ŧ78 mm, 0Ŧ25 mL) f i yfmi° (TEA)Ŧ T ½ c wf¾ ½ ifi ¾i°– f mix  f  xf° f°  fy f f° (9:1 v$v) f¾   °Ŧ T yi  wf¾ 0Ŧ07 – (15%)Ŧ Method B. 3b wf¾ ½ ½f f° i¾f fcc i°–   ½c  ¾cib f 3a, ¾i°– 0Ŧ73 – (1Ŧ92 mm) f 5, 0Ŧ27 – (0Ŧ64 mm) f 3,6- ii -9H-cfbfz 0Ŧ021 – (0Ŧ03 mm) f P (PP3)2C2, 0Ŧ015 – (0Ŧ08 mm) f C I f° 0Ŧ23 – (2Ŧ24 mm, 0Ŧ32 mL) f i yfmi° Ŧ T ½ c wf¾ ½ ifi by ff¾ c m° cmf–f½y ¾i°– f mix  f  xf° f° y fc f (4:1 v$v) f¾   °Ŧ T yi  wf¾ 0Ŧ14 – 1 (24%)Ŧ H NMR (400 MHz, d6-fc ° ) δ (½½m): 10Ŧ76 (¾, 1H, NH), 8Ŧ48-8Ŧ47 (m, 4H), 8Ŧ33 ( , J = 7Ŧ8 Hz, 2H), 7Ŧ69-7Ŧ65 (m, 6H), 7Ŧ61 ( , J = 8Ŧ4 Hz, 2H), 7Ŧ50 ( , J = 1Ŧ7 Hz, 4H), 7Ŧ49–7Ŧ43 13 (m, 6H), 7Ŧ36–7Ŧ32 (m, 2H), 1Ŧ44 (¾, 36H)Ŧ C NMR (100 MHz, d6-fc ° ) δ (½½m): 153Ŧ8, 142Ŧ3, 141Ŧ1, 140Ŧ9, 137Ŧ5, 130Ŧ4, 130Ŧ3, 127Ŧ5, 124Ŧ6, 124Ŧ4, 124Ŧ3, 123Ŧ7, 123Ŧ7, 122Ŧ6, 121Ŧ9, 121Ŧ5, 121Ŧ2, 115Ŧ9, 115Ŧ4, 112Ŧ3, 111Ŧ0, 110Ŧ9, 89Ŧ8, 89Ŧ4, + 35Ŧ8, 31Ŧ7Ŧ MS (MALDI-TO&) (m/z): cfc f C68H63N3 (M ) 921Ŧ5, f ° : 921Ŧ5Ŧ Synthesis of 9-(3,5-di-tert-butylphenyl)-3-[2(trimethylsilyl)ethynyl)]-9H-carbazole (4) 1Ŧ33 – (2Ŧ76 mm) f 2, 0Ŧ10 – (0Ŧ14 mm) f P (PP3)2C2, 0Ŧ07 – (0Ŧ36 mm) f C I w  i¾¾v i° 10 mL f f°y  ¾ TH& °  °i– ° fm¾½  Ŧ T °, 0Ŧ98 – (9Ŧ68 mm, 1Ŧ35 mL) f i yfmi° f° 0Ŧ54 – (5Ŧ50 mm, 0Ŧ78 mL) f y°yim y¾if° i¾¾v i° TH& w  f f° ¾i f m  m½ f  f 10 mi°Ŧ 4 wf¾ ½ ifi fcc i°–   ½c  ¾cib f 2Ŧ T yi  wf¾ 1Ŧ23 1 – (98%)Ŧ H NMR (400 MHz, d6-fc ° ) δ (½½m): 8Ŧ35 ( , J = 1Ŧ6 Hz, 1H), 8Ŧ30 ( , J = 7Ŧ7 Hz, 1H), 7Ŧ67 (, J = 1Ŧ8 Hz, 1H), 7Ŧ52 ( , J1 = 8Ŧ5 Hz, J2 = 1Ŧ6 Hz, 1H), 7Ŧ49–7Ŧ45 (m, 3H), 7Ŧ41 ( , J = 8Ŧ1 Hz, 1H), 7Ŧ38 ( , J = 8Ŧ5 Hz, 1H), 7Ŧ34-7Ŧ30 (m, 1H), 1Ŧ42 (¾, 13 18H), 0Ŧ27 (¾, 9H)Ŧ C NMR (100 MHz, d6-fc ° ) δ (½½m): 153Ŧ8, 142Ŧ3, 141Ŧ4, 137Ŧ3, 130Ŧ6, 127Ŧ6, 125Ŧ0, 124Ŧ1, 123Ŧ6, 122Ŧ6, 121Ŧ8, 121Ŧ5, 121Ŧ3, 115Ŧ1, 110Ŧ9, 110Ŧ8, 107Ŧ4, 92Ŧ2, 35Ŧ8, 31Ŧ7, 0Ŧ2Ŧ HRMS (ESI-MS) (m$z): cfc f C31H38NSi (M + + H) 452Ŧ2768, f ° : 452Ŧ2759Ŧ Synthesis of 9-(3,5-di-tert-butylphenyl)-3-ethynyl-9H-carbazole (5) 1Ŧ2 – (2Ŧ66 mm) f 4 f° 1Ŧ84 – (13Ŧ31 mm) f f°y  ¾ K2CO3 w  i¾¾v i° 180 mL f m f°Ŧ T  fci° mix  wf¾ ¾i f m  m½ f  f 24 Ŧ Af   mi°fi° f   fci°,  ¾v ° wf¾ i¾i ff °   c ½ ¾¾  f°  ½ c wf¾ ½ ifi fcc i°–  1  ½c  ¾cib f 2Ŧ T yi  wf¾ 0Ŧ81 – (80%)Ŧ H NMR (400 MHz, d6-fc ° ) δ (½½m): 8Ŧ38 ( , J = 1Ŧ6 Hz, 1H), 8Ŧ28 ( , J = 7Ŧ8 Hz, 1H), 7Ŧ67 (, J = 1Ŧ8 Hz, 1H), 7Ŧ55 ( , J1 = 8Ŧ5 Hz, J2 = 1Ŧ6 Hz, 1H), 7Ŧ49–7Ŧ45 (m, 3H), 7Ŧ42 ( , J = 8Ŧ3 Hz, 1H), 7Ŧ39 ( , J = 8Ŧ5 Hz, 1H), 7Ŧ34-7Ŧ30 (m, 1H), 3Ŧ57 (¾, 1H), 1Ŧ42 (¾, 13 18H)Ŧ C NMR (100 MHz, d6-fc ° ) δ (½½m): 153Ŧ3, 141Ŧ7, 140Ŧ9, 136Ŧ8, 130Ŧ3, 127Ŧ3, 124Ŧ9, 123Ŧ7, 123Ŧ0, 122Ŧ2, 121Ŧ4, 121Ŧ3, 121Ŧ0, 113Ŧ9, 110Ŧ6, 110Ŧ5, 85Ŧ0, 78Ŧ0, 35Ŧ4, 31Ŧ4Ŧ HRMS + (ESI-MS) (m$z): cfc f C28H30N (M + H) 380Ŧ2373, f ° : 380Ŧ2363Ŧ Instrumentation and methods Siicf –  (–f 62, 60–200 m ¾, 150 Å, A ic) wf¾ ¾ f 1 13 ff¾ c m° cmf–f½yŦ H NMR (400 MHz) f° C NMR (100 MHz) w  c c ° f Vfif° M c y ¾½ cm  Ŧ MALDI-TO& wf¾ ½ fm ° f° A½½i Bi¾y¾ m¾ MDS SCIEX 4800 q i½m °Ŧ Hi–- ¾ i° mf¾¾ ¾½ c¾c½y (HR-MS) wf¾ ½ fm ° f LC$MSD-TO& A–i ° T c°–i ¾ f½½ff ¾ by m f°¾ f   c¾½fy (ESI-MS)  c°iq Ŧ UV-vi¾ ¾½ cf w   –i¾  i° f Vfif° Cfy UV-Vi¾-NIR 500E ¾½ c½m  Ŧ Emi¾¾i° ¾½ cf i° ¾ i° w   c i° f PTI f im   q i½½ wi f 220B fm½ ½w  ¾ ½½y, f 815 ½m i½i   ci° ¾y¾ m f° f & ix 32 ¾fwf ff  xcifi° f 300 °m f° f f c°c °fi° f 10 µM i° icm f° Ŧ P½y¾icf m f¾  m °¾ i°  ¾i ¾f w  ° ° fim¾ ½¾i fm f 1 mM icm f° ¾ i° by ¾½i° cfi°– f 1500 ½m f 20 ¾ f° f 3500 ½m f 10 ¾ fw by 5 mi° f  mf f°° fi°– f 50 °CŦ Q f° m yi  m f¾  m °¾ i° ¾ i° f° i°  ¾i ¾f w   mi° ff  xcifi° f 300 °m ¾i°– ½icfy-mfc ¾ i°¾ f 1,4-bi¾(5-½ °y-2-xfzy)b °z ° (POPOP) f¾  ¾f° f (φ = 0Ŧ93 i° cyc xf° ) fwi°–   ½ 12 m  ¾Ŧ C   ° i°– i° x ¾ w  cfc f ff  xcifi° f 310 °mŦ Cycic vfmm–fm¾ w  cfi   i° f miccm½  -c° ½ °i¾f$–fvf°¾f A fb wi PGSTAT30 q i½m ° f° GPES ¾fwf Ŧ A cyi° icf  -  c c  wf¾ ¾ Ŧ T  f  °c  c wf¾ f M m A–$A–C$KC (3M) m ° i° f L ––i° cf½ify c°fi°i°– f 0Ŧ1 M ¾ i° f  fb yfmm°i m ½ cf (TBAP) i° icm f° Ŧ T c °  f° wki°–  c ¾ w  f ½fi° m ¾½if f° f ½fi° m wi ,  ¾½ civ yŦ A vfmm ic c v ¾ w   c °  q i ¾c ° c° ii°¾, f f ¾cf° f f 100 mV$¾ f° °  f–° fm¾½  Ŧ A ¾ i°¾ w  ½ ½f i° icm f° (1 mM)Ŧ TBAP (A ic,  cc micf –f ) wf¾ ¾ f¾  ¾ ½½i°–  cy Ŧ T i°izfi° ½ °if (IP) vf ¾ w  ¾imf fm  x 0 + °¾  f  fi¾ xi fi° ½ fk f¾ IP = E°¾  - E (&c$&c ) + 0 + 5Ŧ39, w  E (&c$&c ) = +0Ŧ43 V vs A–$A–C$KC (3M) f° w  5Ŧ39 V c ¾½° ¾   fmf ½ °if f  + 13 &c$&c  x c ½ i°  & mi ¾cf Ŧ T  c° fffi°iy vf ¾ (EA) w  cfc f f¾ EA = IP - E–f½Ŧ T ½icf –f½ ° –y (E–f½) wf¾ ¾imf fm λ°¾  f  fb¾½i° ¾½ cfŦ I°izfi° ½ °if wf¾ m f¾  by  ½14 mi¾¾i° i° fi m  Ŧ T ¾fm½ ¾ f   mbiiy m f¾  m °¾ w  ½ ½f by ¾½i°-cfi°–  ¾ i°¾ f  ¾y° ¾iz cm½ ° ¾ °  ½y ¾  fim¾ wi c° civ A fy Ŧ T fy  ick° ¾¾ wf¾ i°  f°– 1Ŧ8-6 µmŦ T  if mbiiy wf¾ m f¾  by  XTO& 15  c°iq Ŧ P¾iiv c°f cf–i°– c f  cic fi  i°¾i  TM fy Ŧ Cf– cfi ¾ w  – ° f f  fy  ¾ ffc by i mi°fi° wi ½ ¾ ¾ f N2 f¾  (½ ¾ fi° wf¾ 2 °¾, wfv  °– 337 °m)Ŧ T fy  ¾ ffc ½ °if c f¾ f¾ f  ¾  f ½ ¾ i mi°fi° wf¾ ½  1–5% f  i°iif ½ °if b f i mi°fi°Ŧ T cf½fcif°c ½b f wf¾ c°° c   wi f q °cy bf°  cm   m f¾   f f  ¾ ffc ½ °if c f¾ , U$ Ŧ T f°¾i im t wf¾  mi° by  ki°k °  c v f  U$  f°¾i ° i°  –-– ¾cf Ŧ 2 T if mbiiy wf¾ cfc f by  fm f µ = d $U0t, w  d i¾  fy  ick° ¾¾ f° U0 i¾  ¾ ffc ½ °if f  mm ° f i mi°fi°Ŧ A&M x½ im °¾ w  c° c ¾i°– f° A&M M im 8 ¾y¾ m ffc  f Nf°¾c½ V  c°ic °i (B k )Ŧ OLED device fabrication and measurements T ¾ b¾f ¾ w  c f° by f¾°ic  fm ° i° fc ° f° i¾½½y fc f° ¾ b¾ q °y i by f °i– ° bwŦ Af  f,  i ¾ ffc ¾ w  ½c ¾¾ wi z°  fm ° f 30 mi°  ¾Ŧ S b¾ q °y, PEDOT:PSS (C vi¾ PV P AI4083 fm HŦCŦ Sfck, fi  f 0Ŧ45 μm) wf¾ ¾½i°-cf f 4500 ½m (ick° ¾¾ f ° 25 °m) °  ITO ¾ ffc f° f y bfk f 120 °C f 20 mi°Ŧ Af  f, ¾fi°– fm f ¾ i° f 10 m–$mL, 3a wf¾ ¾½i° cf¾ fm iff  ° ¾v °¾ °  PEDOT:PSS fy  f° ¾ cc ¾¾iv y  f f 50 °C f 5 mi°Ŧ Sfm½ ¾ w  f°¾f  i° f °i– ° fi –v bx w  10 °m f TPBi, 1 °m f Li& f° 100 °m f A w  ½¾i by  mf vf½fi° °  fciv fy  °  i– vfc mŦ T vic ¾ w  ½  i° f ¾fm½   f ½ c  m fm xy– ° f° mi¾  f° fw c°fci°–  m f m f¾ i°–Ŧ T ff civ f f f 2 fc c  wf¾ ∼9 mm Ŧ T c  ° °¾iy-vf– f°  mi°f°c -vf– ff w  ¾im f°  ¾y fcq i by f K i y 2400 °i (c  °) f° f K°icf-Mi°f LS-100 ( mi°f°c )Ŧ 3 4 5 6 7 8 9 Acknowledgements &i°f°cif ¾ ½½ fm  Ministerio de Economía y Competitividad (CTQ2012-36074) i¾ –f f y fck°w – Ŧ MR i¾ –f f  f  –f° ADR fm Universitat de Barcelona (UB)Ŧ EP f°k¾ MINECO ½j c CTQ2013-47183 f¾ w  f¾  S v  Ocf Exc  °c Acc ifi° 2014–2018 (SEV-20130319)Ŧ EP i¾ f¾ –f f   ICIQ f° ICREA f c°micf ¾ ½½Ŧ EM& fck°w – ¾ MINECO f  ½j c MAT2012-31570 f° Rfm° y Cfjf f w¾i½ (RyC-201006787)Ŧ VŦ Gfi i¾, D ½fm ° f  Si Sf E c°ic, Vi°i ¾ U°iv ¾iy, i¾ f°k f  m f¾  m °¾ f i°izfi° ½ °if¾Ŧ Notes and references 1 2 XŦ Yf°–, XŦ X f° GŦ Z , J. 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