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[d5dt02441b1.pdf](https://mdr.nims.go.jp/filesets/2cec1044-6942-4066-a88e-496c913f04a9/download)
## Creator
[Koki Matsushima](https://orcid.org/0009-0001-0220-6075), [Takuya Ohmi](https://orcid.org/0000-0001-9761-134X), Wataru Taniguchi, Shoya Nagano, Tomoya Fukui, [Takanori Fukushima](https://orcid.org/0000-0001-5586-9238), Muhammad Awais, [Makhsud Saidaminov](https://orcid.org/0000-0002-3850-666X), [Masaki Azuma](https://orcid.org/0000-0002-8378-321X), [Takafumi Yamamoto](https://orcid.org/0000-0002-7960-1014)
## Rights
[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)
## Other metadata
[Tunable optical properties in the (110) p -oriented layered halide perovskite FA 4 Pb 2 I 7.5 (SCN) 0.5 by Br substitution](https://mdr.nims.go.jp/datasets/a13ff5ab-f43a-4cf1-a8da-d5f64e64776f)
## Fulltext
Supporting Information Tunable Optical Properties in (110)p-oriented Layered Halide Perovskite FA4Pb2I7.5(SCN)0.5 by Br Substitution Koki Matsushimaa,b, Takuya Ohmib,c,d, Wataru Taniguchib, Shoya Naganob, Tomoya Fukuie,f, Takanori Fukushimae,f, Muhammmad Awaisd, Makhsud Saidaminovd, Masaki Azumab,f,g, and Takafumi Yamamoto *a,b a. Department of Chemistry, Graduate School of Science, Kyoto university, Kitashirakawa Oiwake-cho, Sakyoku, Kyoto, 606-8502, Japan. b. Materials and Structures Laboratory, Institute of Integrated Research, Institute of Science Tokyo, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa, 226-8501, Japan. c. Advanced Phosphor Group, Research Center for Electric and Optical Materials, National Institute for Material Science (NIMS), 1-1, Namiki, Tsukuba 305-0044, Japan. d. Department of Electrical & Computer Engineering, University of Victoria, 3800 Finnerty Road, Victoria, British Columbia V8P 5C2, Canada. e. Laboratory for Chemistry and Life Science, Institute of Innovative Research, Institute of Science Tokyo, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8501, Japan. f. Research Center for Autonomous Systems Materialogy (ASMat), Institute of Integrated Research, Institute of Science Tokyo, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa, 226-8501, Japan. g. Kanagawa Institute of Industrial Science and Technology, 705-1 Shimoimaizumi, Ebina 243-0435, Japan Supplementary Information (SI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2025Supplementary Note 1 Characterization of FA4Pb2(Br,SCN)8 single crystal We synthesized a fully Br-substituted FA4Pb2I7.5(SCN)0.5 single crystal to clarify its structure. The single crystals were obtained by the solid-state reaction method under FA+ and SCN− excess conditions as reported in FA4Pb2I7.5(SCN)0.5.1 After heating, the sample was a paste that separated into white and light yellowish-green layers in the glass tube (Figure S3a). The obtained crystals were picked up from the paste into the Fluorolube® oil because of their air sensitivity. The crystal was plate-shaped with 0.1 × 0.04 × 0.03 mm3 sizes. The crystals showed green PL emission by exposing blue light (Figure S4), but collection of the spectroscopic data was difficult due to the instability. The single crystal X-ray analysis of the data at 293(2) K revealed that the compound has a monoclinic structure (Space group: P21/c) with a = 6.0372(3) Å, b = 25.564(2) Å, c = 8.6039(8) Å, and β = 94.902(6)°. Details of crystallographic information are shown in Supporting information (Tables S4-8). The determined crystal structure (Figure S2) is a (110)p-oriented layered perovskite structure (Figure 1). Although the structure is similar to FA4Pb2I7.5(SCN)0.5, the crystal symmetry is reduced from orthorhombic Cmmm to monoclinic P21/c by Br substitution. The size difference between I− and Br− may induce this symmetry reduction. The atomic ratio of Br02/S02 = 0.951(7)/ 0.049(7) and Br04/S04 = 0.954(8)/ 0.046(8) at the octahedral terminate site was obtained from single crystal analysis, leading the chemical composition of FA4Pb2Br7.81(3)(SCN)0.19(3). This sulfur ratio value is slightly smaller than the iodide counterpart (I/S = 0.857(7)/0.143(7)).1 We note that the (110)p-oriented layered perovskites FA4Pb2Br8 (FA2PbBr4) without SCN− was previously synthesized by solution method.2 The crystal structures of these compounds are reported with different cell symmetry and lattice parameters at 100 K; triclinic phase of P-1 with a = 8.5642(17) Å; b = 11.884(2) Å; c = 14.312(3) Å, α = 65.92°; β = 73.01°; γ = 83.76° and monoclinic phase of P21/c with a = 13.1313(9) Å; b = 7.9763(6) Å; c = 11.7972(8); β = 91.52°.2 Therefore, the obtained single crystals in this report indeed include SCN− in the structure. Figure S1. Crystal structure of FA4Pb2I7.5(SCN)0.5 with Cmmm, reported in the reference.1 Figure S2. Crystal structure of FA4Pb2Br7.81(3)(SCN)0.19(3) with P21/c, obtained from single crystal XRD. The ellipsoids correspond to 50% probability thermal ellipsoids derived from anisotropic displacement parameters. Figure S3. (a) Photograph of the product sealed in a glass tube after heating. (b) Microscopic image of obtained single crystals. Figure S4. Photograph of the single crystals under UV irradiation. Figure S5. Le Bail refinement result of x = 0 at 300 K. Black marks, red line, and gray line represent observed, calculated, and different, respectively, and green ticks show peak positions. GOF, Rwp, Rp are 1.80, 4.64%, and 6.30%, respectively. Figure S6. Le Bail refinement result of x = 0.25 at 300 K. Black marks, red line, and gray line represent observed, calculated, and different, respectively, and green ticks show peak positions. GOF, Rwp, Rp are 1.60, 6.18%, and 4.61%, respectively. Figure S7. Le Bail refinement result of x = 0.5 at 300 K. Black marks, red line, and gray line represent observed, calculated, and different, respectively, and green ticks show peak positions. GOF, Rwp, Rp are 1.46, 5.96%, and 4.53%, respectively. Figure S8. Le Bail refinement result of x = 0.75 at 300 K. Black marks, red line, and gray line represent observed, calculated, and different, respectively, and green ticks show peak positions. GOF, Rwp, Rp are 1.99, 7.06%, and 5.23%, respectively. Figure S9. Le Bail refinement result of x = 1 at 300 K. Black marks, red line, and gray line represent observed, calculated, and different, respectively, and green ticks show peak positions. GOF, Rwp, Rp are 2.80, 9.72%, and 6.93%, respectively. Figure S10. SEM image and EDX mapping of x = 0.25 thin film on ITO substrate. Figure S11. SEM image of x = 0.25 thin film on ITO substrate. Table S1. Atomic concentration at four spots shown in Figure S11. Element at. % 1 2 3 4 (substrate) Average between 1 to 3 Si 18.0 13.7 18.9 32.8 - In 33.4 24.9 40.7 59.5 - Pb 9.7 12.9 8.1 0.8 10.2 I 27.3 35.8 22.2 1.0 28.4 Br 11.6 12.7 10.1 6.0 11.5 Figure S12. SEM image and EDX mapping of x = 0.5 thin film on ITO substrate. Figure S13. SEM image of x = 0.5 thin film on ITO substrate. Table S2. Atomic concentration at four spots shown in Figure S13. Element at. % 1 2 3 4 (substrate) Average between 1 to 3 Si 7.9 8.0 7.1 22.3 - In 29.3 31.7 28.0 54.8 - Pb 12.9 12.3 13.3 4.4 12.8 I 23.9 23.3 25.2 6.4 24.1 Br 26.1 24.8 26.4 12.2 25.8 Figure S14. SEM image and EDX mapping of x = 0.75 thin film on ITO substrate. Figure S15. SEM image of x = 0.5 thin film on ITO substrate. Table S3. Atomic concentration at four spots shown in Figure S13. Element at. % 1 2 3 4 (substrate) Average between 1 to 3 Si 5.3 4.7 1.7 35.3 - In 25.7 25.2 14.7 58.7 - Pb 14.8 15.4 18.7 0.1 16.3 I 12.4 13.4 14.9 0.0 13.6 Br 41.8 41.3 50.0 5.9 44.4 Figure S16. The Tauc’s plot of FA4Pb2I7.5(SCN)0.5 (x = 0). Band gap is estimated to 2.18 eV. Figure S17. The Tauc’s plot of FA4Pb2(Br0.25I0.75)7.5(SCN)0.5 (x = 0.25). Band gap is estimated to 2.22 eV. Figure S18. The Tauc’s plot of FA4Pb2(Br0.5I0.5)7.5(SCN)0.5 (x = 0.5). Band gap is estimated to 2.42 eV. Figure S19. The Tauc’s plot of FA4Pb2(Br0.75I0.25)7.5(SCN)0.5 (x = 0.75). Band gap is estimated to 2.59 eV. Figure S20. The Tauc’s plot of FA4Pb2Br7.5(SCN)0.5 (x = 1). Band gap is estimated to 2.81 eV. Figure S21. The result of absolute PL measurement for x = 0, the date represents the film fabrication date. Table S4. Crystallographic data obtained by single crystal X-ray structure analysis. Estimated standard deviations are shown in parentheses. Empirical formula C8N16Pb4Br15.2S0.8 Formula weight 2389.28 Temperature /K 293(2) Crystal system monoclinic Space group P21/c a /Å 6.0372(3) b /Å 25.564(2) c /Å 8.6039(8) α /° 90 β /° 94.902(6) γ /° 90 Volume /Å3 1323.05(19) Z 1 ρcalc g/cm3 2.999 μ /mm-1 24.219 F (0 0 0) 1033.0 Crystal size /mm3 0.1 × 0.04 × 0.03 Radiation Mo Kα (λ = 0.71073) 2θ range for data collection /° 4.752 to 52.738 Index ranges -7 ≤ h ≤ 5, -31 ≤ k ≤ 31, -10 ≤ l ≤ 10 Reflections collected 13195 Independent reflections 2719 [Rint = 0.0391, Rsigma = 0.0323] Data / Restraints / Parameters 2719 / 0 / 109 Goodness-of-fit on F2 1.053 Final R indexes [I ≥ 2σ(I)] R1 = 0.0415, wR2 = 0.1031 Final R indexes [all data] R1 = 0.0577, wR2 = 0.1102 Largest diff. peak / hole /e Å-3 1.15 / –1.88 Table S5. Fractional atomic coordinates and equivalent isotropic displacement parameters (Å2 ) obtained by single crystal X-ray structure analysis. Ueq is defined as 1/3 of the trace of the orthogonalized UIJ tensor. Estimated standard deviations are shown in parentheses. Atom x y z Ueq /Å2 Occupancy Pb01 0.43167(4) 3363.9(2) 5276.2(3) 0.04761(15) 1 Br02 0.39169(19) 0.41393(4) 0.27565(13) 0.0754(5) 0.951(7) Br03 0.43216(16) 0.25000(4) 0.27963(11) 0.0810(3) 1 Br04 0.4617(2) 0.41783(4) 0.77229(14) 0.0903(6) 0.954(8) Br05 0.93095(13) 0.33959(5) 0.53156(16) 0.0990(5) 1 N5 0.8440(30) 0.4798(6) 0.4580(20) 0.170(7) 1 N8 0.0340(50) 0.1820(13) 0.4560(30) 0.251(15) 1 C3 1 0.5 0.5 0.161(12) 1 N2 -0.1910(60) 0.1617(11) 0.6120(40) 0.286(18) 1 C4 -0.0800(40) 0.1775(10) 0.5370(30) 0.154(8) 1 N1 0.0450(30) 0.5301(12) 0.0740(40) 0.244(13) 1 C2 1570(140) 5030(20) -0.0070(50) 0.200(30) 0.5 S02 0.39169(19) 0.41393(4) 0.27565(13) 0.0754(5) 0.049(7) S04 0.4617(2) 0.41783(4) 0.77229(14) 0.0903(6) 0.046(8) Table S6. Anisotropic displacement parameters (Å2) obtained by single crystal X-ray structure analysis. The anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…]. Estimated standard deviations are shown in parentheses. Atom U11 /Å2 U22 /Å2 U33 /Å2 U23 /Å2 U13 /Å2 U12 /Å2 Pb01 0.03508(19) 0.0494(2) 0.0580(2) 0.00096(13) 0.00164(13) 0.00095(10) Br02 0.0843(8) 0.0669(7) 0.073.(7) 0.0127(5) -0.0018(5) 0.0055(4) Br03 0.09.6(8) 0.0693(7) 0.0796(7) -0.0182(5) 0.0041(6) -0.0053(5) Br04 0.1129(10) 0.0756(9) 0.0809(9) -20.2(6) 0.0003(6) 0.0009(6) Br05 0.0341(5) 0.1130(11) 0.1497(13) 0.0242(7) 0.0071(6) 0.0033(4) N5 0.120(10) 0.154(11) 0.241(18) -0.039(12) 0.038(12) -0.068(10) N8 0.270(30) 0.270(30) 0.230(30) -0.001(19) 0.140(20) -0.110(20) C3 0.090(16) 0.250(40) 0.140(20) -0.040(20) 0.032(15) -0.020(20) N2 0.290(30) 0.310(40) 0.290(30) 0.007(19) 0.220(30) 0.033(19) C4 0.170(20) 0.120(15) 0.180(30) 0.005(14) 0.046(19) 0.002(12) N1 0.107(14) 0.310(30) 0.310(30) 0.140(30) -0.050(16) -0.037(15) C2 0.360(100) 0.130(30) 0.110(30) 0.050(20) 0.080(50) 0.070(50) S02 0.0843(8) 0.0669(7) 0.0733(7) 0.0127(5) -0.0018(5) 0.0055(4) S04 0.1129(10) 0.0756(9) 0.0809(9) -0.0202(6) 0.0003(6) 0.0009(6) Table S7. Bond lengths obtained by single crystal X-ray structure analysis. Estimated standard deviations are shown in parentheses. Atom Atom Length /Å Pb01 Br02 2.9321(10) Pb01 Br031 3.0949(9) Pb01 Br03 3.0711(9) Pb01 Br04 2.9553(11) Pb01 Br05 3.0127(8) Pb01 Br052 3.0271(8) Pb01 S02 2.9321(10) Pb01 S04 2.9553(11) N5 C3 1.109(14) N8 C4 1.03(3) N2 C4 1.06(3) N1 C23 1.55(8) N1 C2 1.23(4) C2 C23 1.91(16) 1+X,1/2-Y,1/2+Z; 2-1+X,+Y,+Z; 3-X,1-Y,-Z Table S8. Bond angle obtained by single crystal X-ray structure analysis. Estimated standard deviations are shown in parentheses. Atom Atom Atom Angle /˚ Atom Atom Atom Angle /˚ Br02 Pb01 Br031 174.56(3) Br05 Pb01 Br052 176.65(5) Br02 Pb01 Br03 88.70(3) S02 Pb01 Br03 88.70(3) Br02 Pb01 Br04 92.67(4) S02 Pb01 Br05 90.52(3) Br02 Pb01 Br052 88.33(3) S02 Pb01 S04 92.67(4) Br02 Pb01 Br05 90.52(3) S04 Pb01 Br03 176.27(3) Br03 Pb01 Br031 88.484(10) S04 Pb01 Br05 88.42(4) Br04 Pb01 Br031 90.42(3) Pb01 Br03 Pb013 179.53(4) Br04 Pb01 Br03 176.27(3) Pb01 Br05 Pb014 176.65(5) Br04 Pb01 Br052 88.49(4) N5 C3 N55 180 Br04 Pb01 Br05 88.42(4) N8 C4 N2 164(4) Br05 Pb01 Br03 88.11(3) C2 N1 C26 86(6) Br052 Pb01 Br03 95.02(3) N1 C2 N16 94(6) Br052 Pb01 Br031 87.28(3) N1 C2 C26 54(3) Br05 Pb01 Br031 94.04(3) N16 C2 C26 40(4) 1+X,1/2-Y,1/2+Z; 2-1+X,+Y,+Z; 3+X,1/2-Y,-1/2+Z; 41+X,+Y,+Z; 52-X,1-Y,1-Z; 6-X,1-Y,-Z Reference 1 T. Ohmi, J. R. Neilson, W. Taniguchi, T. Fukui, T. Nagase, Y. Haruta, M. I. Saidaminov, T. Fukushima, M. Azuma and T. Yamamoto, ACS Mater Lett, 2024, 6, 1913–1919. 2 S. A. Fateev, A. A. Petrov, E. I. Marchenko, Y. V. Zubavichus, V. N. Khrustalev, A. V. Petrov, S. M. Aksenov, E. A. Goodilin and A. B. Tarasov, Chemistry of Materials, 2021, 33, 1900–1907. Supporting Information