Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 27 Electronic Supplementary Information bis-zn II salphen complexes bearing pyridyl functionalized ligands for efficient organic light-emitting diodes (LEDs) Jiang Zhao, a Feifan Dang, a Boao Liu, a Yong Wu, a Xiaolong Yang, a Guijiang Zhou, *a Zhaoxin Wu, * b Wai-Yeung Wong *c a ME Key Laboratory for onequilibrium Synthesis and Modulation of Condensed Matter, Institute of Chemistry for ew Energy Material, Department of Chemistry, School of Science, State Key Laboratory for Mechanical Behavior of Materials, Xi an Jiaotong University, Xi an 749, P. R. China. E-mail: zhougj@mail.xjtu.edu.cn. Fax: +86-29-8266-394 b Key Laboratory for Physical Electronics and Devices of the Ministry of Education, Faculty of Electronic and Information Engineering, Xi an Jiaotong University Xi an 749, P. R. China. E- mail: zhaoxinwu@mail.xjtu.edu.cn c Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, P. R. China. E-mail: wai-yeung.wong@polyu.edu.hk
Contents Synthesis detials for intermediate compounds. Fig. S Key front molecular orbital patterns of the bis-zn II salphen complexes with expanded view. Fig. S2 Current density voltage luminance (J V L) curves for the LEDs. Fig. S3 EL efficiency luminance curves for the LEDs. Fig. S4 Current density voltage luminance (J V L) curves and EL efficiency luminance curves for the related LEDs. 2
Synthesis detials for intermediate compounds. S P Si,4-dioxane, Pd(dppfc)Cl 2 KAc, C 24h B B B B B S P Si B-S B-P B-Si B(H) 2 HCl Pd(PPh 3 ) 4, THF, 2M a 2 C 3, C BS CH 3 Cl, o C-RT 4-TPA -- Scheme S Synthetic scheme for intermediate compounds. Preparation of bis-schiff Base ligand (L-SB): To a solution of,2,4,5-benzenntetramine tetrahydrochloride (3 mg,.4577 mmol) in 2 ml anhydrous methanol was added of 3,5-di-tertbutyl-2-hydroxybenzaldehyde (47 mg, 2.4 mmol). After 8 h continuously stirring, the yellow precipitate was collected and washed with anhydrous methanol and dried under vacuum. The yellow solid was obtained. (Yield: 92%, 423 mg); H MR (4 MHz, CDCl 3, δ): 3.47 (s, 4H), 8.78 (s, 4H), 7.47 (d, J = 2.4 Hz, 4H), 7.27 (d, J = 2.4 Hz, 4H), 7.6 (s, 2H),.46 (s, 36H),.34 (s, 36H); 3 C 3
MR ( MHz, CDCl 3, δ): 64.65, 58.63, 4.57, 4.5, 37.24, 28.5, 26.9, 8.32,.4, 35.2, 34.9, 3.45, 29.42. Preparation of Zn-C: To a solution of bis-schiff Base compound ( mg, 9.97 mmol) in 2 ml mixture of chloroform and methane (2 : ) was added of Zn(Ac) 2 H 2 (67 mg, 2.989 mmol). After stirring at room temperature for 8 h, the solvent was evaporated and the red solid was dissolved in Dichloromethane, the insoluble residual was filtered off, after evaporating dichloromethane of the filtrate, the red Zn-C was obtained by recrystallization in Acetonitrile. (Yield: 65%, 73 mg); H MR (4 MHz, Acetone-d 6, δ): 9.25 (s, 4H), 8.5 (s, 2H), 7.47 (d, J = 4 Hz, 4H), 7.9 (d, J = 2.4 Hz, 4H),.55 (s, 36H),.34 (s, 36H). General procedures for the synthesis of borate compounds: Under a 2 atmosphere, bis- (pinacolato)diboro (.4 g, 5.5 mmol), the aromatic bromide prepared from literature reported (5 mmol), KAc (.54 g, 5.5 mmol) and Pd(dppfc)Cl 2 (.8 g, 5 mol-%) were heated to o C in 25 ml degassed,4-dioxane for 24 h. After cooling to room temperature, the mixture was extracted with dichloromethane, the organic phase was dried over anhydrous a 2 S 4 and the solvent was evaporated under reduced pressure. The residual was chromatographed using appropriate eluent to produce the title product. B-S:.62 g white solid was obtained by using PE : EA = ( 5 : ) as eluent (Yield: 93%);. H MR (4 MHz, CDCl 3, δ): 7.94 7.92 (m, 6 H), 7.57 7.53 (m, H), 7.48 (t, J = 7.2 Hz, 2 H),.32 (s, 2 H); 3 C MR ( MHz, CDCl 3 ): δ (ppm) 43.6, 4.46, 35.46, 33.8, 29.25, 27.63, 26.6, 84.4, 24.8; FAB-MS (m/z): 344 [M] +. Elemental analysis calcd (%) for C 8 H 2 B 4 S: C 62.8, H 6.5; found: C 62.74, H 5.98. B-P:.58 g brown oil was obtained by using EA : DCM = : as eluent (Yield: 78%); H MR (4 MHz, CDCl 3 ): δ (ppm) 7.88 7.85 (m, 2 H), 7.68 7.6 (m, 6 H), 7.54 7.5 (m, 2 H), 7.45 7.4 (m, 4 H),.32 (s, 2 H); 3 C MR ( MHz, CDCl 3 ): δ (ppm) 35.24, 34.52, 34.4, 34.22, 4
32.55, 32.7, 3.97, 3.93, 3.5, 3.6, 3.7, 28.48, 28.36, 84.2, 24.75; 3 P MR (62 MHz, CDCl3): δ (ppm) 29.2; FAB-MS (m/z): 44 [M] +. Elemental analysis calcd (%) for C 24 H 26 B 3 P: C 7.3, H 6.48; found: C 7.9, H 6.39. B-Si:.8 g white solid was obtained by using EA : DCM = : as eluent (Yield: 78%); H MR (4 MHz, CDCl 3, δ) 7.8 (d, J = 7.6 Hz, 2 H), 7.56 (t, J = 6.8 Hz, 8 H), 7.43 (t, J = 7.6 Hz, 3 H), 7.37 (t, J = 7.2 Hz, 6 H),.32 (s, 2 H); 3 C MR ( MHz, CDCl 3 ): δ (ppm) 37.94, 36.52, 35.83, 34.9, 34.2, 29.75, 28.8, 83.98, 25.; FAB-MS (m/z): 462 [M] +. Elemental analysis calcd (%) for C 3 H 3 B 2 Si: C 77.9, H 6.76; found: C 77.79, H 6.68. Preparation of 4-TPA: Under a 2 atmosphere, 4-bromopyridine hydrochloride (.97 g, 5.5 mmol), (4-(diphenylamino)phenyl)boronic acid (.45 g, 5 mmol), tetrabutylammonium iodide (2.32 g, 5.5 mmol) and Pd(PPh 3 ) 4 (.289 g, 5% mmol) were heated to o C in a mixture of ml 2M a 2 C 3 and 25 ml degassed THF for 24 h. After cooling to room temperature, the mixture was extracted with dichloromethane, the organic phase was dried over a 2 S 4 and the solvent was removed under reduced pressure. The residue was obtained as a crude product, which was chromatographed on a silica column using PE : EA = 2 : as eluent to produce a pure product. (Yield: 62%, 998 mg); H MR (4 MHz, CDCl 3, δ): 8.62 (d, J = 6 Hz, 2H), 7.52 (d, J = 8.8 Hz, 4H), 7.3 (t, J = 8.4 Hz, 4H), 7.5 7.3 (m, 6H), 7.8 (t, J = 7.2 Hz, 2H); 3 C MR ( MHz, CDCl 3, δ): 5.6, 48.92, 47.63, 47.22, 3.9, 29.4, 27.6, 24.96, 23.58, 22.89, 2.86; FAB-MS (m/z): 322 [M] +. Elemental analysis calcd (%) for C 23 H 8 2 : C 85.68, H 5.63, 8.69; found: C 85.55, H 5.59,, 8.58. Preparation of --: Under a 2 atmosphere, 4-TPA (.8 g, 2.485 mmol), BS (.876 g, 5.93 mmol) and 3 drops AcH was stirred in 25 ml chloroform at room temperature for h. After 8h continuously stirring at 5 o C, 2 ml water was added, the mixture was extracted with dichloromethane, the organic phase was dried over anhydrous a 2 S 4 and the solvent was 5
evaporated under reduced pressure. The target product obtained by flash silica column using DCM : EA = 4 : as eluent. (Yield: 97%,.57 g); H MR (4 MHz, CDCl 3, δ): 8.63 (d, J = 4.4 Hz, 2H), 7.54 (d, J = 6.8 Hz, 2H), 7.47 (d, J = 5.6 Hz, 2H), 7.39 (d, J = 8.8 Hz, 2H), 7.2 (d, J = 8.8 Hz, 2H), 7. (d, J = 8.8 Hz, 4H); 3 C MR ( MHz, CDCl 3, δ): 5.26, 47.89, 47.32, 45.96, 32.57, 32.29, 27.95, 26.8, 23.67, 2.96, 6.36; FAB-MS (m/z): 478 [M] +. Elemental analysis calcd (%) for C 23 H 6 2 2 : C 57.53, H 3.36, 5.85; found: C 57.39, H 3.27, 5.72 Fig. S Key front molecular orbital patterns of the bis-zn II salphen complexes with expanded view. 6
Current density (ma cm -2 ) Current density (ma cm -2 ) 5 5 5 5 Device A2 Device A3 4 6 8 2 Device C2 Device C3 4 6 8 2 Current density (ma cm -2 ) Current density (ma cm -2 ) 5 5 Device B Device B3 2 4 6 8 2 4 5 5 Device D Device D3 2 4 6 8 2 Fig. S2 Current density voltage luminance (J V L) curves for the LEDs. 7
Device A2 Device A3 / (cd A -2 /lm W - )... (%) / (cd A -2 /lm W - )... (%).. Device B Device B3 / (cd A -2 /lm W - ).... (%) / (cd A -2 /lm W - ).... (%) Device C2 Device C3 / (cd A -2 /lm W - )... (%) / (cd A -2 /lm W - )... (%).. Device D Device D3 / (cd A -2 /lm W - )... (%) / (cd A -2 /lm W - )... (%).. Fig. S3 EL efficiency luminance curves for the LEDs. 8
Current density (ma cm -2 ) / (cd A -2 /lm W - ) 5 5 (a) 4 6 8 2 4. (a). (%) Current density (ma cm -2 ) / (cd A -2 /lm W - ) 5 5. (b) 4 6 8 2 4 6 (b). (%).... Fig. S4 Current density voltage luminance (J V L) curves and EL efficiency luminance curves for LEDs. (a) Device based on Zn-C with 6 wt-% doping level, (b) Device based with Zn- neat film. Reference. G.-J. Zhou, Q. Wang, C.-L. Ho, W.-Y. Wong, D.-G. Ma, L.-X. Wang and Z.-Y. Lin, J. Mater. Chem.,, 2, 7472. 9