aa family of highly efficient CuI-based lighting phosphors prepared by a systematic, bottom-up synthetic approach Wei Liu #,a, Yang Fang #,a, George Z. Wei a, Simon J. Teat b, Kecai Xiong a, Zhichao Hu a, William P. Lustig a and Jing Li*,a a Department of Chemistry and Chemical Biology, Rutgers University, 610 Taylor Road, Piscataway, NJ, 08854, USA b Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA Supporting Information S1
TABLE OF CONTENT S1. Crystallographic data and selected structure plots... 3 S2. Powder X-ray diffraction (PXRD) patterns 8 S3. Crystal images of selected compounds. 12 S4. Thermogravimetric (TG) analysis of selected compounds... 16 S5. Electronic band structure (BS) and density of states (DOS) calculations of selected structures. 20 S6. Molecular orbital (MO) energy calculations of the ligands. 26 S7. Absorption, photoluminescence spectra, decay profile and related color quality parameters of selected compounds.. 28 S8. Prototype LED devices made of selected phosphors and PXRD of white phosphor.. 33 S9. Elemental analysis results of selected compounds.. 35 S10. References.. 36 S2
S1. Crystallographic data and selected structure plots. Table S1. Summary of crystal data of compounds 3, 4, 5, 6, 7. Compoun d 0D-Cu 2I 2(3-Clpy) 4 (3) 0D-Cu 2I 2(tpp) 2 (3-pc) 2 (4) 0D-Cu 2I 2(tpp) 2 (4,6-dm-pm) 2 (5) 1D-Cu 2I 2(tpp) 2 (bpp) (6) 1D-Cu 2I 2(tpp) 2 (4,4 -dps) (7) Empirical Formula C 20H 16C l4cu 2I 2N 4 C 24H 22CuINP C 48H 46Cu 2I 2N 4P 2 C 49H 44Cu 2I 2N 2 P 2 C 92H 76Cu 4I 4N 4P 4 S 2 FW 835.05 545.83 1121.71 1103.68 2187.32 Space P-1 C2/c P-1 P2 1/c C2/c Group a (Å) 7.8020(4) 25.9199(15) 9.3886(3) 13.2151(5) 26.0237(10) b (Å) 8.6628(4) 14.9505(9) 11.5199(4) 13.5525(5) 9.3012(4) c (Å) 9.4711(5) 11.5468(7) 11.5849(4) 25.3512(9) 20.2799(8) ( ) 90.919(2) 90 79.129(2) 90 90 ( ) 94.251(3) 97.115(2) 69.089(2) 94.613(2) 117.533(2) ( ) 102.751(2) 90 72.439(2) 90 90 V (Å 3 ) 622.28(5) 4440.1(5) 1111.29(7) 4525.6(3) 4352.8(3) Z 1 8 1 4 2 T (K) 100(2) 150(2) 100(2) 298(2) 230(2) λ(å) 0.7749 0.71073 0.71073 0.7749 0.7085 R 1 0.0388 0.0735 0.0421 0.0435 0.0503 wr 2 0.1046 0.1725 0.0692 0.0652 0.0775 S3
Table S2. Summary of crystal data of compounds 9, 11, 12, 14. Compound 1D-Cu 2I 2(tpp) 2(5- Br-pm) (9) 1D-Cu 2I 2(5-mepm) 2 (11) 1D-Cu 2I 2(5-Br-pm) 2 (12) 2D-Cu 2I 2(3,3 - bpy) 2 (14) Empirical C 80H 66Br 2Cu 4I 4N 4P C 5H 6CuIN 2 C 4H 3BrCuIN 2 C 10H 8CuIN 2 Formula 4 FW 2128.82 284.56 349.43 346.62 Space C2/c Cmca Cmca P2 1/n Group a (Å) 17.2033(7) 8.4063(4) 8.437(2) 9.4898(13) b (Å) 17.7719(7) 21.6785(10) 21.875(6) 9.7370(18) c (Å) 14.9470(6) 16.5331(7) 16.757(4) 12.2051(18) ( ) 90 90 90 90 ( ) 122.467(2) 90 90 111.784(2) ( ) 90 90 90 90 V (Å 3 ) 3855.6(3) 3012.9(2) 3092.6(14) 1047.2(3) Z 2 16 16 4 T (K) 100(2) 100(2) 296(2) 150(2) λ(å) 0.7293 0.71073 0.71073 0.71073 Rp 0.0295 0.0384 0.0305 0.0445 Rwp 0.0478 0.0678 0.0655 0.0675 S4
Figure S1. Structures of selected 0D clusters: 0D-Cu2I2(3-pc)4 (1) and 0D-Cu2I2(3-Cl-py)4 (3). Figure S2. Structure of single-chain 1D-Cu2I2(tpp)2(4,4 -bpy) (8). S5
Figure S3. Structure of double-chain 1D-Cu2I2(5-me-pm)2 (11). S6
Figure S4. Structure of 2D-Cu2I2(3,3 -bpy)2 (14). S7
S2. Powder X-ray diffraction (PXRD) patterns. Figure S5. PXRD patterns of compounds 1 to 5. From bottom to top: simulated 1, experimental 1, simulated 2, experimental 2, simulated 3, experimental 3, simulated 4, experimental 4, simulated 5 and experimental 5. S8
Figure S6. PXRD patterns of compounds 6 to 11. From bottom to top: simulated 6, experimental 6, simulated 7, experimental 7, simulated 8, experimental 8, simulated 9, experimental 9, simulated 10, experimental 10, simulated 11, and experimental 11. S9
Figure S7. PXRD patterns of compounds 12 to 16. From bottom to top: simulated 12, experimental 12, simulated 13, experimental 13, simulated 14, experimental 14, simulated 15, experimental 15, simulated 16, and experimental 16. S10
Figure S7a. PXRD patterns of the products for the synthesis of compound 12: simulated 12 (black), single-phased 12 prepared by precursor method (red), simulated 1D-CuI(5-Br-pm) structure which is made of CuI staircase chain module (green), two-phase mixture of 1D-CuI(5-Br-pm) (major) and 12 (minor) obtained using CuI/KI as starting material (blue). S11
S3. Crystal images of selected compounds. Figure S8. Crystal image of 0D-Cu2I2(3-Cl-py)4 (3). Figure S9. Crystal image of 0D-Cu2I2(tpp)2(4,6-dm-pm)2 (5). S12
Figure S10. Crystal image of 1D-Cu2I2(tpp)2(4,4 -dps) (7). Figure S11. Crystal image of 1D-Cu2I2(tpp)2(5-Br-pm) (9). S13
Figure S12. Crystal image of 1D-Cu2I2(5-me-pm)2 (11). Figure S13. Crystal image of 1D-Cu2I2(5-Br-pm)2 (12). S14
Figure S14. Crystal image of 2D-Cu2I2(3,3-bpy)2 (14). S15
S4. Thermogravimetric (TG) analysis of selected compounds. Figure S15. TG plots of 1 (black), 2 (red), 3 (blue), 4 (green), 5 (pink). S16
Figure S16. TG plots of 6 (black), 7 (red), 8 (blue), 9 (green), 11 (pink). S17
Figure S17. TG plots of 13 (black), 14 (red), 15 (blue), 16 (green). S18
Figure S18. TG plot of 17. S19
S5. Electronic band structure (BS) and density of states (DOS) calculations of selected structures. The BS and DOS of selected structures were calculated by CASTEP package 1 (Materials Studio 4.4). Generalized gradient approximations (GGA) with Perdew-Burke-Ernzerhof (PBE) exchangecorrelation functional (xc) were used in all calculations. While it is well known DFT tends to give underestimated band gaps the differences between the calculated and experimental values show excellent agreement, as shown in Table S3 below. Table S3. Comparison of theoretical band gaps from CASTEP with the experimental band gap values of selected compounds. Compound Calcd. band gap (ev) Exptl. band gap (ev) Difference between exptl. and calcd. band gap (ev) 0D-Cu2I2(tpp)2(3-pc)4 1.815 3.0 1.18 0D-Cu2I2(3,5-dm-py)4 1.708 2.8 1.10 0D-Cu2I2(3-Cl-py)4 1.147 2.5 1.35 1D-Cu2I2(tpp)2(4,4 -bpy) 1.237 2.4 1.16 1D-Cu2I2(5-Br-pm)2 0.868 2.1 1.23 2D-Cu2I2(bpe)2 1.530 2.8 1.27 2D-Cu2I2(4,4 -dps)2 1.195 2.5 1.30 S20
Figure S19. Calculated density of states (DOS) of 0D-Cu2I2(3,5-dm-py)4 (2) by DFT method: total DOS (black); Cu 3d orbitals (light blue); I 5p orbitals (red); C 2p orbitals (grey); N 2p orbitals (blue). S21
Figure S20. Calculated density of states (DOS) of 0D-Cu2I2(3-Cl-py)4 (3) by DFT method: total DOS (black); Cu 3d orbitals (light blue); I 5p orbitals (red); C 2p orbitals (grey); N 2p orbitals (blue). S22
Figure S21. Calculated density of states (DOS) of 0D-Cu2I2(tpp)2(3-pc)4 (4) by DFT method: total DOS (black); Cu 3d orbitals (light blue); I 5p orbitals (red); C from 3-pc 2p orbitals (dark grey); C from tpp 2p orbitals (light grey); N 2p orbitals (blue); P 3p orbitals (orange). S23
Figure S22. Calculated density of states (DOS) of 1D-Cu2I2(5-Br-pm)2 (12) by DFT method: total DOS (black); Cu 3d orbitals (light blue); I 5p orbitals (red); C 2p orbitals (grey); N 2p orbitals (blue). S24
Figure S23. Calculated density of states (DOS) of 2D-Cu2I2(bpe)2 (13) by DFT method: total DOS (black); Cu 3d orbitals (light blue); I 5p orbitals (red); C 2p orbitals (grey); N 2p orbitals (blue). S25
S6. Molecular orbital (MO) energy calculations of the ligands. DGDZVP 2,3 and 6-311++G(3df,3pd) 4-11 were used for the calculation of the HUMO/LUMO energy of the ligands and the results are listed in Table S4. There is a correlation between electronic affinity of the functional groups and the energy level, as shown in the table. Table S4. Calculated HOMO-LUMO energy levels of ligands. Basis Set DGDZVP 6-311++G(3df,3pd) Name Structure HOMO (ev) LUMO (ev) HOMO (ev) LUMO (ev) triphenylphosphine (tpp) -5.962-0.874-6.032-0.985 3,5-dimethylpyridine (3,5-dmpy) -6.869-0.933-6.924-1.039 3-picoline (3-pc) -7.056-0.982-7.089-1.073 pyridine (py) -7.175-1.041-7.213-1.120 1,2-bis(4-pyridyl)ethane (bpe) -7.243-1.172-7.262-1.244 4,6-dimethyl-pyridimine (4,6- dm-pm) -7.001-1.208-7.021-1.257 1,3-bis(4-pyridyl)propane (bpp) 3-cloro-pyridine (3-Cl-py) -7.173-1.163-7.191-1.258-7.340-1.428-7.361-1.473 S26
5-methyl-pyrimidine (5-me-pm) -7.087-1.452-7.098-1.501 3,3 -bipyridine (3,3 -bpy) -6.915-1.621-6.926-1.621 4,4 -dipyridyl sulfide (4,4 -dps) pyrazine (pz) -6.734-1.706-6.723-1.790-7.146-1.857-7.125-1.795 5-bromopyrimidine (5-Br-pm) -7.550-1.943-7.538-1.970 4,4'-bipyridine (4,4 -bpy) -7.399-2.044-7.386-2.016 S27
S7. Absorption, photoluminescence spectra, decay profile and related color quality parameters of selected compounds. Figure S24. Optical absorption spectra of the precursor 1 in solid state (black) and in acetone (red), along with that of acetone (blue). S28
Figure S25. Luminescence decay profile (log scale) of 1D-Cu2I2(tpp)2(bpp) (6). S29
Figure S26. Luminescence decay profile (log scale) of 2D-Cu2I2(4,4 -dps)2 (15). Table S5. Luminescence lifetime (τ) of selected structures. Structures Band gap λem (nm) IQY(%) Lifetime (µs) (ev) 1D-Cu2I2(tpp)2(bpp) (6) 2.8 458 91.7±0.5 13.1 1D-Cu2I2(tpp)2(4,4 -bpy) (8) 2.5 540 76.2±0.9 4.0 1D-Cu2I2(tpp)2(pz) (10) 2.1 631 26.1±0.3 1.7 2D-Cu2I2(4,4 -dps)2 (15) 2.5 547 70.8±0.3 6.5 S30
Figure S27. PXRD patterns of 2D-Cu2I2(4,4 -dps)2 (15) after various treatments. From bottom to top: simulated, freshly made, in air for six month, under blue light for a week, heated at 80 C for a week. S31
Figure S28. Emission spectrum of 2D-Cu2I2(4,4 -dps)2 (15) after various treatments. From bottom to top: freshly made (black), in the air for six month (red), under blue light for a week (blue), at 80 C for a week (cyan). λex is 455 nm. Table S6. CCT, CRI and CIE of compound 17. Quantum yield (%) CCT (K) CRI CIE 62.6±0.2 4512 73.8 0.31, 0.36 S32
S8. Prototype LED devices made of selected phosphors and PXRD of white phosphor. Figure S29. Schematic of the remote-phosphor design (left) and prototype LED bulbs made of selected CuI based hybrid phosphors (right). S33
Figure S30. PXRD patterns of compound 17 as-synthesized by mixing 6 and 8 in solid state (cyan, middle) and after being dispersed in water for 2 h (blue, top). Both match almost perfectly with the combined pattern of simulated 6 (pink, bottom) and 8 (red, bottom). S34
S9. Elemental analysis results of selected compounds. Table S7. Summary of elemental analysis (Robertson Microlit Lab). Compound C% H% N% 0D-Cu 2I 2(tpp) 2(3-pc) 4 Calculated 52.76 4.06 2.56 Experimental 52.68 4.32 2.53 1D-Cu 2I 2(5-me-pm) 2 Calculated 21.09 2.11 9.84 Experimental 21.10 2.16 9.55 2D-Cu 2I 2(3,3 -bpy) 2 Calculated 34.62 2.31 8.08 Experimental 35.73 2.56 7.68 S35
S10. References (1) Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. J.; Refson, K.; Payne, M. C. Z Kristallogr 2005, 220, 567. (2) Godbout, N.; Salahub, D. R.; Andzelm, J.; Wimmer, E. Canadian Journal of Chemistry 1992, 70, 560. (3) Sosa, C.; Andzelm, J.; Elkin, B. C.; Wimmer, E.; Dobbs, K. D.; Dixon, D. A. The Journal of Physical Chemistry 1992, 96, 6630. (4) Gordon, M. S. Chemical Physics Letters 1980, 76, 163. (5) Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; DeFrees, D. J.; Pople, J. A. The Journal of Chemical Physics 1982, 77, 3654. (6) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. V. R. Journal of Computational Chemistry 1983, 4, 294. (7) Frisch, M. J.; Pople, J. A.; Binkley, J. S. The Journal of Chemical Physics 1984, 80, 3265. (8) Binning, R. C.; Curtiss, L. A. Journal of Computational Chemistry 1990, 11, 1206. (9) Blaudeau, J.-P.; McGrath, M. P.; Curtiss, L. A.; Radom, L. The Journal of Chemical Physics 1997, 107, 5016. (10) Rassolov, V. A.; Pople, J. A.; Ratner, M. A.; Windus, T. L. The Journal of Chemical Physics 1998, 109, 1223. (11) Ditchfield, R.; Hehre, W. J.; Pople, J. A. The Journal of Chemical Physics 1971, 54, 724. S36