We acknowledge support from the University of St Andrews, the China Scholarship Council (studentship to YYG).Three new 1D chain structure type hybrid organic–inorganic lead(II) halides are presented: IQPbBr3, QPbBr3 and QPbI3, templated by large organic cations, isoquinolinium ([IQ+] = protonated isoquinoline) and its isomer quinolonium ([Q+] = protonated quinoline). All three compounds possess the same generic formula as cubic perovskite, ABX3, but adopt different structures. IQPbBr3 adopts a 1D face-sharing single chain hexagonal perovskite structure type, and the other two, QPbBr3 and QPbI3, adopt a non-perovskite structure which is built from 1D edge-sharing octahedral double chains. Crystal structures and preliminary photophysical properties are discussed. Two of them have lower bandgaps than the other reported materials with the same structure type, indicating the value of further exploratory studies for these types of materials.PostprintPostprintPeer reviewe

Guo,  Yuan-Yuan

Lightfoot, Philip

Dalton Transactions

English

Three new 1D chain structure type hybrid organic–inorganic lead(II) halides are presented: IQPbBr3, QPbBr3 and QPbI3, templated by large organic cations, isoquinolinium ([IQ+] = protonated isoquinoline) and its isomer quinolonium ([Q+] = protonated quinoline). All three compounds possess the same generic formula as cubic perovskite, ABX3, but adopt different structures. IQPbBr3 adopts a 1D face-sharing single chain hexagonal perovskite structure type, and the other two, QPbBr3 and QPbI3, adopt a non-perovskite structure which is built from 1D edge-sharing octahedral double chains. Crystal structures and preliminary photophysical properties are discussed. Two of them have lower bandgaps than the other reported materials with the same structure type, indicating the value of further exploratory studies for these types of materials

Guo, Yuan-Yuan

University of St. Andrews - Pure

Structural diversity of lead halide chain compounds, APbX<sub>3</sub>, templated by isomeric molecular cations

We acknowledge support from the University of St Andrews, the China Scholarship Council (studentship to YYG).Three new 1D chain structure type hybrid organic–inorganic lead(II) halides are presented: IQPbBr3, QPbBr3 and QPbI3, templated by large organic cations, isoquinolinium ([IQ+] = protonated isoquinoline) and its isomer quinolonium ([Q+] = protonated quinoline). All three compounds possess the same generic formula as cubic perovskite, ABX3, but adopt different structures. IQPbBr3 adopts a 1D face-sharing single chain hexagonal perovskite structure type, and the other two, QPbBr3 and QPbI3, adopt a non-perovskite structure which is built from 1D edge-sharing octahedral double chains. Crystal structures and preliminary photophysical properties are discussed. Two of them have lower bandgaps than the other reported materials with the same structure type, indicating the value of further exploratory studies for these types of materials.Peer reviewe

St Andrews Research Repository

Structural Diversity of Lead Halide Chain Compounds, APbX3, Templated by Isomeric Molecular Cations Yuan-Yuan Guo and Philip Lightfoot* School of Chemistry and EaStChem, University of St Andrews, St Andrews, KY16 9ST, UK;  E-Mail: pl@st-andrews.ac.uk (PL)    Supplementary Information   Figure S1. The full-range and expanded P-XRD data for IQPbBr3 at room temperature. Figure S2. The full-range and expanded P-XRD data for QPbBr3 at room temperature. Figure S3. The full-range and expanded P-XRD data for QPbI3 at room temperature. Figure S4. The nature of the distortions within the inorganic PbX6 octahedra of the three compounds. Figure S5. Thermal Gravimetric Analysis (TGA) of IQPbBr3, QPbBr3 and QPbI3.  Table S1. Crystal and Structure Refinement Data for the three compounds at 173 K. Table S2. Selected bond lengths (Å) and bond angles (°) for IQPbBr3 at 173 K and 298 K. Table S3. Selected bond lengths (Å) and bond angles (°) for QPbBr3 at 173 K and 298 K. Table S4. Selected bond lengths (Å) and bond angles (°) for QPbI3 at 173 K and 298 K. Table S5. Hydrogen bond lengths (Å) and angles (°) for IQPbBr3, QPbBr3 and QPbI3 at 173 K.  Figure S1. The full-range (a) and expanded (b) P-XRD data for IQPbBr3 at room temperature, the corresponding colours represent the experimental (black) and the calculated (red) pattens.    Figure S2. The full-range (a) and expanded (b) P-XRD data for QPbBr3 at room temperature, the corresponding colours represent the experimental (black) and the calculated (red) pattens.  Figure S3. The full-range (a) and expanded (b) P-XRD data for QPbI3 at room temperature, the corresponding colours represent the experimental (black) and the calculated (red) pattens.   Figure S4. The nature of the distortions within the inorganic PbX6 octahedra of the three compounds at 298 K. (a) Pb(1)Br6 octahedra for IQPbBr3, (b) Pb(2)Br6 octahedra for IQPbBr3, (c) PbBr6 octahedra for QPbBr3, (d) PbI6 octahedra for QPbI3.   Figure S5. Thermal Gravimetric Analysis (TGA) of IQPbBr3, QPbBr3 and QPbI3.    Table S1. Single crystal and structure refinement data for IQPbBr3, QPbBr3 and QPbI3 at 173 K.   IQPbBr3 QPbBr3 QPbI3 Formula C9H8NPbBr3 C9H8NPbBr3 C9H8NPbI3 Formula weight 577.08 577.08 718.05 Colour/Habit Colorless/Chip Colorless/Prism Yellow/Prism Crystal size (mm3) 0.32 × 0.24 × 0.09 0.25 × 0.06 × 0.04 0.32 × 0.09 × 0.05 Crystal system Orthorhombic Monoclinic Monoclinic Space group Pbca P21/n C2/c a (Å) 21.1904(15)  4.3397(2)  25.767(2)  b (Å) 7.7771(5)  22.5309(17)  4.6411(4)  c (Å) 30.828(2)  13.0048(10)  25.931(2)  α (°) 90 90 90 β (°) 90 98.941(6) 115.396(7) γ (°) 90 90 90 V (Å3) 5080.5(6)  1256.12(15)  2801.3(4) Z 16 4 8 ρcalc (g/cm3) 3.018 3.052 3.405 μ (mm-1) 22.684 22.937 18.625 F(000) 4096 1024 2480 Reflns collected 47986 9972 12590 Independent reflns 5808 2192 3132 0.099 0.1118 0.086 Goodness of Fit 1.072 0.944 0.909 Final R indices (I > 2σ(I)) R1 = 0.0397 R1 = 0.0349 R1 = 0.0400 wR2 = 0.0966 wR2 = 0.0768 wR2 = 0.0954 Largest diff. peak/hole (e Å-3) 2.408/-2.586 1.955/-1.922 2.360/-1.679     Table S2. Selected bond lengths (Å) and bond angles (°) for IQPbBr3 at 173 K and 298 K. Temperature 173 K 298 K Pb(1)-Br(1)  2.9955(7) 3.0034(11) Pb(1)-Br(1)#1  3.0752(8) 3.0763(11) Pb(1)-Br(2)  3.2403(8) 3.2299(12) Pb(1)-Br(2)#1  2.8753(8) 2.8846(12) Pb(1)-Br(3)  2.9449(8) 2.9535(11) Pb(1)-Br(3)#1  3.0364(8) 3.0398(11) Pb(2)-Br(4)  3.0923(8) 3.0837(11) Pb(2)-Br(4)#2  2.9921(8) 3.0088(11) Pb(2)-Br(5)  2.8328(8) 2.8425(11) Pb(2)-Br(5)#2 3.3111(8) 3.2973(12) Pb(2)-Br(6)  3.0377(8) 3.0295(11) Pb(2)-Br(6)#2  2.9515(8) 2.9704(11) Br(2)#1-Pb(1)-Br(3) 95.50(2) 95.80(3) Br(2)#1-Pb(1)-Br(1) 93.95(2) 94.23(3) Br(3)-Pb(1)-Br(1) 88.38(2) 88.14(3) Br(2)#1-Pb(1)-Br(3)#1 84.87(2) 84.86(3) Br(3)-Pb(1)-Br(3)#1 94.52(3) 94.55(4) Br(2)#1-Pb(1)-Br(1)#1 82.36(2) 82.49(3) Br(1)-Pb(1)-Br(1)#1 91.78(2) 92.00(3) Br(3)#1-Pb(1)-Br(1)#1 85.30(2) 85.29(3) Br(3)-Pb(1)-Br(2) 80.21(2) 80.45(3) Br(1)-Pb(1)-Br(2) 77.81(2) 78.14(3) Br(3)#1-Pb(1)-Br(2) 103.56(2) 102.93(3) Br(1)#1-Pb(1)-Br(2) 101.91(2) 101.24(3) Br(5)-Pb(2)-Br(6)#2 92.21(2) 93.52(3) Br(5)-Pb(2)-Br(4)#2 94.04(2) 95.05(3) Br(6)#2-Pb(2)-Br(4)#2 88.90(2) 88.23(3) Br(5)-Pb(2)-Br(6) 85.20(2) 85.37(3) Br(6)#2-Pb(2)-Br(6) 94.89(3) 95.01(4) Br(5)-Pb(2)-Br(4) 84.15(2) 84.34(3) Br(4)#2-Pb(2)-Br(4) 90.64(2) 90.97(3) Br(6)-Pb(2)-Br(4) 85.53(2) 85.81(3) Br(6)#2-Pb(2)-Br(5)#2 78.60(2) 78.73(3) Br(4)#2-Pb(2)-Br(5)#2 78.02(2) 78.18(3) Br(6)-Pb(2)-Br(5)#2 103.33(2) 101.83(3) Br(4)-Pb(2)-Br(5)#2 103.90(2) 103.28(3) Pb(1)-Br(1)-Pb(1)#2 79.66(2) 79.53(3) Pb(2)-Br(4)-Pb(2)#1 79.43(2) 79.33(3) Pb(1)#2-Br(2)-Pb(1) 78.72(2) 78.77(3) Pb(2)-Br(5)-Pb(2)#1 78.11(2) 78.22(3) Pb(2)#1-Br(6)-Pb(2) 80.96(2) 80.81(3) Pb(1)-Br(3)-Pb(1)#2 81.09(2) 80.91(3) Symmetry transformations used to generate equivalent atoms:  #1 -x+1/2,y+1/2,z    #2 -x+1/2,y-1/2,z      Table S3. Selected bond lengths (Å) and bond angles (°) for QPbBr3 at 173 K and 298 K. Temperature 173 K 298 K Pb(1)-Br(1)  2.8241(9) 2.8247(6) Pb(1)-Br(2)#1  2.9985(9) 3.0046(6) Pb(1)-Br(2)  3.0201(9) 3.0267(6) Pb(1)-Br(3)  3.0317(9) 3.0352(6) Pb(1)-Br(3)#1 3.2822(9) 3.2890(6) Pb(1)-Br(3)#2  3.0713(9) 3.0766(6) Br(1)-Pb(1)-Br(2)#1 90.42(3) 90.37(2) Br(1)-Pb(1)-Br(2) 88.91(3) 89.17(2) Br(2)-Pb(1)-Br(3) 87.04(2) 86.43(2) Br(2)#1-Pb(1)-Br(2) 92.28(2) 92.68(2) Br(1)-Pb(1)-Br(3) 91.97(3) 92.27(2) Br(2)#1-Pb(1)-Br(3) 89.10(2) 88.67(2) Br(1)-Pb(1)-Br(3)#2 90.47(3) 91.05(2) Br(2)#2-Pb(1)-Br(3)#1 92.06(3) 92.20(2) Br(2)-Pb(1)-Br(3)#2 87.97(2) 87.51(2) Br(3)-Pb(1)-Br(3)#1 92.07(2) 91.38(2) Br(3)#1-Pb(1)-Br(3)#2 87.12(2) 87.19(2) Br(3)-Pb(1)-Br(3)#2 90.64(2) 91.11(2) Pb(1)#2-Br(2)-Pb(1) 92.28(2) 92.68(2) Pb(1)#2-Br(3)-Pb(1)#1 92.88(2) 93.57(2) Pb(1)#2-Br(3)-Pb(1) 87.93(2) 88.62(2) Pb(1)-Br(3)-Pb(1)#1 90.64(2) 91.11(2) Symmetry transformations used to generate equivalent atoms:  #1 x-1,y,z    #2 x+1,y,z     Table S4. Selected bond lengths (Å) and bond angles (°) for QPbI3 at 173 K and 298 K. Temperature 173 K 298 K Pb(1)-I(1)  3.0001(7) 2.9956(6) Pb(1)-I(2)  3.2051(6) 3.2092(5) Pb(1)-I(2)#1  3.2945(6) 3.2996(5) Pb(1)-I(3)  3.2174(6) 3.2207(5) Pb(1)-I(3)#1  3.2732(6) 3.2749(5) Pb(1)-I(3)#2 3.5061(6) 3.5212(5) I(1)-Pb(1)-I(2) 90.87(2) 91.19(1) I(1)-Pb(1)-I(3) 91.76(2) 92.40(1) I(2)-Pb(1)-I(3) 89.92(2) 89.67(1) I(1)-Pb(1)-I(3)#1 92.89(2) 93.08(1) I(3)-Pb(1)-I(3)#1 91.29(2) 91.53(1) I(1)-Pb(1)-I(2)#1 92.00(2) 91.88(1) I(2)-Pb(1)-I(2)#1 91.12(2) 91.28(1) I(3)#1-Pb(1)-I(2)#1 87.42(2) 87.20(1) I(2)-Pb(1)-I(3)#2 89.16(2) 89.13(1) I(3)-Pb(1)-I(3)#2 92.04(2) 91.71(1) I(3)#1-Pb(1)-I(3)#2 87.19(2) 86.69(1) I(2)#1-Pb(1)-I(3)#2 84.21(2) 84.04(1) Pb(1)-I(2)-Pb(1)#2 91.12(2) 91.28(1) Pb(1)-I(3)-Pb(1)#2 91.29(2) 91.53(1) Pb(1)-I(3)-Pb(1)#3 92.81(2) 93.31(1) Pb(1)#2-I(3)-Pb(1)#3 87.96(2) 88.29(1) Symmetry transformations used to generate equivalent atoms:  #1 x,y+1,z    #2 x,y-1,z    #3 x-1/2,-y+1/2,-z+1    Table S5. Hydrogen bond lengths (Å) and angles (°) for IQPbBr3, QPbBr3 and QPbI3 at 173 K. APbX3 D-H...A d(D-H) d(H...A) d(D...A) <(DHA)  N(1)-H(2)...Br(1) 0.86 3.13 3.537(8) 111.8   N(1)-H(2)...Br(1)#1 0.86 3.08 3.694(9) 129.9 IQPbBr3  N(1)-H(2)...Br(6)#3 0.86 2.98 3.613(8) 132.3   N(2)-H(10)...Br(3) 0.86 3.10 3.413(8) 104.4   N(2)-H(10)...Br(4) 0.86 2.72 3.462(9) 145.5       QPbBr3 N(1)-H(1)...Br(1) 0.86 2.50 3.324(8) 161.9       QPbI3  N(1)-H(1)...I(1) 0.86 2.93 3.604(8) 136.5    N(1)-H(1)...I(1)#3 0.86 3.24 3.829(8) 128.0 Symmetry transformations used to generate equivalent atoms:  #1 -x+1/2,y+1/2,z        #3 x,-y+1/2,z+1/2    (IQPbBr3);               #3 -x+1,y,-z+3/2    (QPbI3) 