Supporting Information

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1 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

2 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 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

3 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 Space P-1 C2/c P-1 P2 1/c C2/c Group a (Å) (4) (15) (3) (5) (10) b (Å) (4) (9) (4) (5) (4) c (Å) (5) (7) (4) (9) (8) ( ) (2) (2) ( ) (3) (2) (2) (2) (2) ( ) (2) (2) V (Å 3 ) (5) (5) (7) (3) (3) Z T (K) 100(2) 150(2) 100(2) 298(2) 230(2) λ(å) R wr S3

4 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 Space C2/c Cmca Cmca P2 1/n Group a (Å) (7) (4) 8.437(2) (13) b (Å) (7) (10) (6) (18) c (Å) (6) (7) (4) (18) ( ) ( ) (2) (2) ( ) V (Å 3 ) (3) (2) (14) (3) Z T (K) 100(2) 100(2) 296(2) 150(2) λ(å) Rp Rwp S4

5 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

6 Figure S3. Structure of double-chain 1D-Cu2I2(5-me-pm)2 (11). S6

7 Figure S4. Structure of 2D-Cu2I2(3,3 -bpy)2 (14). S7

8 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

9 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

10 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

11 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

12 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

13 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

14 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

15 Figure S14. Crystal image of 2D-Cu2I2(3,3-bpy)2 (14). S15

16 S4. Thermogravimetric (TG) analysis of selected compounds. Figure S15. TG plots of 1 (black), 2 (red), 3 (blue), 4 (green), 5 (pink). S16

17 Figure S16. TG plots of 6 (black), 7 (red), 8 (blue), 9 (green), 11 (pink). S17

18 Figure S17. TG plots of 13 (black), 14 (red), 15 (blue), 16 (green). S18

19 Figure S18. TG plot of 17. S19

20 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) D-Cu2I2(3,5-dm-py) D-Cu2I2(3-Cl-py) D-Cu2I2(tpp)2(4,4 -bpy) D-Cu2I2(5-Br-pm) D-Cu2I2(bpe) D-Cu2I2(4,4 -dps) S20

21 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

22 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

23 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

24 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

25 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

26 S6. Molecular orbital (MO) energy calculations of the ligands. DGDZVP 2,3 and 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 G(3df,3pd) Name Structure HOMO (ev) LUMO (ev) HOMO (ev) LUMO (ev) triphenylphosphine (tpp) ,5-dimethylpyridine (3,5-dmpy) picoline (3-pc) pyridine (py) ,2-bis(4-pyridyl)ethane (bpe) ,6-dimethyl-pyridimine (4,6- dm-pm) ,3-bis(4-pyridyl)propane (bpp) 3-cloro-pyridine (3-Cl-py) S26

27 5-methyl-pyrimidine (5-me-pm) ,3 -bipyridine (3,3 -bpy) ,4 -dipyridyl sulfide (4,4 -dps) pyrazine (pz) bromopyrimidine (5-Br-pm) ,4'-bipyridine (4,4 -bpy) S27

28 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

29 Figure S25. Luminescence decay profile (log scale) of 1D-Cu2I2(tpp)2(bpp) (6). S29

30 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) ± D-Cu2I2(tpp)2(4,4 -bpy) (8) ± D-Cu2I2(tpp)2(pz) (10) ± D-Cu2I2(4,4 -dps)2 (15) ± S30

31 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

32 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± , 0.36 S32

33 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

34 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

35 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 Experimental D-Cu 2I 2(5-me-pm) 2 Calculated Experimental D-Cu 2I 2(3,3 -bpy) 2 Calculated Experimental S35

36 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, (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, (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, (8) Binning, R. C.; Curtiss, L. A. Journal of Computational Chemistry 1990, 11, (9) Blaudeau, J.-P.; McGrath, M. P.; Curtiss, L. A.; Radom, L. The Journal of Chemical Physics 1997, 107, (10) Rassolov, V. A.; Pople, J. A.; Ratner, M. A.; Windus, T. L. The Journal of Chemical Physics 1998, 109, (11) Ditchfield, R.; Hehre, W. J.; Pople, J. A. The Journal of Chemical Physics 1971, 54, 724. S36