[Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2): Synthesis and Geometric and Electronic Structures

Size: px

Start display at page:

Download "[Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2): Synthesis and Geometric and Electronic Structures"

Godwin Stevenson
5 years ago
Views:

1 SUPPORTING INFORMATION [Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2): Synthesis and Geometric and Electronic Structures Lakshmi V. Nair, a Sakiat Hossain, b Shota Wakayama, a Shunjiro Takagi, a Mahiro Yoshioka, a Juri Maekawa, a Atsuya Harasawa, a Bharat Kumar, a Yoshiki Niihori, a Wataru Kurashige, a and Yuichi Negishi a,b,* a Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo , Japan. b Photocatalysis International Research Center, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba , Japan. Corresponding Author negishi@rs.kagu.tus.ac.jp; Tel: ; Fax: Table Table S1. Potential Assignment of the FT-IR Spectral Peaks for the [Pt 17 (CO) 12 (PPh) 8 ] n+ Cluster wavenumber (cm 1 ) Assignment a wavenumber (cm 1 ) Assignment a 3069 ν(c H) 1325 ν(c C) aromatic 3052 ν(c H) 1307 combination tone 3028 ν(c H) 1268 δ(c H) ip 3013 combination tone 1199 combination tone 3001 combination tone 1182 combination tone 1974 (terminal CO) 1157 δ(c H) ip 1941 (terminal CO) 1119 combination tone 1895 combination tone 1069 δ(c H) ip 1812 combination tone 1027 δ(c H) ip 1742 (μ 2 -CO) 999 ring breathing mode 1584 ν(c C) aromatic 913 δ(c H) oop 1571 ν(c C) aromatic 849 δ(c H) oop 1542 combination tone 742 δ(c H) oop ring 1478 ν(c C) aromatic 695 δ(c H) oop ring 1434 ν(c C) aromatic 539 overtone 1378 combination tone ν: stretching, δ: deformation, ip: in-plane, oop: out-of-plane a See refs. 1 and 2. S1

2 2. Additional Figures Figure S1. Laser-fluence dependence of the positive-ion MALDI mass spectra of a mixture of Pt clusters protected by CO and PPh 3 (Figure 1(a)). The peaks at m/z ~ 3100 are probably attributed to the fragments of the clusters with m/z ~ 4200 or Figure S2. Positive-ion ESI mass spectrum of a mixture of Pt clusters protected by CO and PPh 3 (Figure 1(a)). S2

3 Figure S3. Isotope distribution of the peak group of [Pt 17 (CO) 12 (PPh 3 ) 8 ] + observed in Figure 2(a) together with calculated patterns. Figure S4. Negative-ion ESI mass spectrum of as-prepared Pt 17 (CO) 12 (PPh 3 ) 8 (Figure 1(b) and 2(a)). S3

4 Figure S5. Assignment of the peak indicated by an asterisk (*) in Figure 2(b). Figure S6. Positive-ion ESI mass spectra of [Pt 17 (CO) 12 (PPh 3 ) 8 ] n+ (n = 1, 2) (a) before and (b) after exchange of the counter anion. S4

5 Figure S7. Photographs of crystals of (a) [Pt17(CO)12(PPh3)8][SbF6] and (b) [Pt17(CO)12(PPh3)8][(SbF6)2]. Figure S8. Reduction-time dependence of the MALDI mass spectra of the product for reduction times of (a) 10, (b) 20, and (c) 30 min. S5

6 Figure S9. Stability of a mixture of [Pt 17 (CO) 12 (PPh 3 ) 8 ][SbF 6 ] and [Pt 17 (CO) 12 (PPh 3 ) 8 ][(SbF 6 ) 2 ] in dichloromethane solution. 3. Crystals 3.1. Crystal Data Cluster 1 ([Pt 17 (CO) 12 (PPh 3 ) 8 ][SbF 6 ]): C 156 H 110 F 6 O 12 P 8 Pt 17 Sb; Mr ; triclinic, P-1 (No. 2); a = (5) Å, b = (5) Å, c = (5) Å, α = (4), β = (4), γ = (4), V = 3783(2) Å 3 ; T = 100 K; Z = 1; Z' = 1; µ (Mo K α ) = mm 1 ; A total of reflections were measured ( θ ) and 8851 unique reflections (R int = ) were used in all calculations. The final wr2 of all data was and R1 was (I>2σ (I)). Cluster 2 ([Pt 17 (CO) 12 (PPh 3 ) 8 ][(SbF 6 ) 2 ]): C 80 H 60 F 4.5 O 6.5 P 4 Pt 8.5 Sb; Mr ; triclinic, P-1 (No. 2); a = (2) Å, b = (2) Å, c = (2) Å, α = (10), β = (2), γ = (2) ; V = (9) Å 3 ; T = 100 K; Z= 2; Z' = 1; µ (Mo K α ) = mm 1 ; A total of reflections were measured ( θ ) and 9075 unique reflections (R int = ) were used in all calculations. The final wr2 of all data was and R1 was (I>2σ (I)). Crystal data and structural refinement parameters are listed in Table S2 S Structure Quality Indicators and Refinement Details The absorption coefficients of cluster 1 and 2 were and , respectively. The minimum (maximum) transmission of cluster 1 and 2 was (0.7458) and (0.7458), respectively. An initial model of each crystal structure of the clusters containing Pt 17 P 8 and a few carbon atoms was solved by the intrinsic phasing method 3 and the remaining atoms were generated via difference Fourier synthesis. Subsequently, total crystal structures were refined by the full-matrix least-squares method against F 2 by SHELXL-2014/7 4 using the Olex-2 software 5 platform. We also checked other possible space groups using PLATON addsym ; 6 in both cases, it showed that our space group assignment was correct. During overall refinement, several restraints and constraints (SADI, RIGU, SIMU, DFIX, AFIX 66, and EADP) were used. Hydrogen atoms were placed at calculated positions, with the exception of disordered H atoms, and their positions were refined with a riding model. In cluster 1, all the metal, phosphorous, and fluorine atoms were refined anisotropically. In cluster 2, metal (all the Pt and Sb1) and fluorine atoms (F1, F2, F3, F4, F5, and F6) were refined anisotropically. Remaining atoms of both clusters were refined isotropically. In cluster 1, one [SbF 6 ] was not located in the ideal symmetry position. However, when its occupancy was refined, it was found to be very close to 0.5, the R-factor decreased by one unit (from 5.23 to 4.24), and S6

7 the geometry became quite good. Therefore, the occupancy of this anion was fixed to 0.5. We also checked the electron count corresponding to [SbF 6 ] using option SQUEEZE of program PLATON 5 by first squeezing all the Q peaks and then squeezing Q peaks other than those of [SbF 6 ]. The electron count obtained after this treatment was 1.25 times higher than that of the expected electron count of one [SbF 6 ]. Thus, we believe that cluster 1 had one [SbF 6 ] counter anion. This is consistent with ICP-MS data. In the case of cluster 2, we could clearly assign one [SbF 6 ] counter anion (labeled as Sb1 in the cif) per cluster. However, when its occupancy was refined, it was found to be very close to 0.5, the R-factor decreased by 0.64 (from 7.35 to 6.71), and the geometry became quite good. Thus, the occupancy of [SbF 6 ] (labeled as Sb1 in the cif) was fixed at 0.5. This cluster contained one high-q peak at 22 e Å 3 that was located at an inversion center. We could not perfectly model [SbF 6 ] from surrounding Q peaks. In the absence of any idealized geometry of [SbF 6 ], it was difficult to model [SbF 6 ] with good O h symmetry and good thermal ellipsoids. To aid visual understanding, we did not treat electron densities contributing to the disordered [SbF 6 ] and other diffused solvents using option SQUEEZE of program PLATON 5. We also tried to assign the Q peak at 22 e Å 3 as a chloride anion or sodium cation but assignment as Sb of [SbF 6 ] was better. Thus, we assigned it as a half-occupied Sb (labeled as Sb2 in the cif file) located at an inversion center. Therefore, we believe that cluster 2 has two [SbF 6 ] per cluster cation. This is consistent with ESI mass analysis. Also, we could model only one diethyl ether solvent molecule using the idealized geometry from Guzei s idealized molecular geometry library Tabulated Crystal Data Table S2. Crystal Data and Structural Refinement Parameters Identification code cluster 1 cluster 2 Empirical formula C 156 H 110 F 6 O 12 P 8 Pt 17 Sb C 80 H 60 F 4.5 O 6.5 P 4 Pt 8.5 Sb Formula weight Temperature/K Crystal system triclinic triclinic Space group P-1 P-1 a/å (5) (2) b/å (5) (2) c/å (5) (2) α/ (4) (10) β/ (4) (2) γ/ (4) (2) Volume/Å (2) (9) Z 1 2 ρ calc g/cm μ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) MoKα (λ = ) 2Θ range for data collection/ to to Index ranges -15 h 15, -16 k 15, -17 l h 16, -16 k 16, -10 l 18 Reflections collected Independent reflections 8851 [R int = , R sigma = ] 9075 [R int = , R sigma = ] Data/restraints/parameters 8851/165/ /179/498 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R 1 = , wr 2 = R 1 = , wr 2 = Final R indexes [all data] R 1 = , wr 2 = R 1 = , wr 2 = Largest diff. peak/hole / e Å / /-6.38 Table S3. Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å ) for Cluster 1. U eq is defined as one third of the trace of the orthogonalized U IJ tensor. Atom x y z U(eq) Pt (2) S7

8 C1 1265(15) 1185(14) 6752(13) 36(6) Pt (5) (5) (5) 13.58(19) C2 6395(17) 9613(16) 8569(15) 53(3) Pt (5) (5) (4) 14.30(19) C3 6948(18) 9215(16) 9168(16) 53(3) Pt (5) (5) (5) 13.76(19) Pt (5) (5) (5) 16.7(2) Pt (5) (5) (5) 14.86(19) Pt (5) (5) (5) 13.96(19) Pt (5) (5) (5) 17.6(2) C4 6657(18) 8407(16) 9272(16) 53(3) Pt (5) (5) (5) 15.13(19) P1 3081(3) 6718(3) 3116(3) 15.3(11) P2 2035(3) 2870(3) 3192(3) 17.4(12) P3 4007(3) 7631(3) 7490(3) 18.2(12) P4 2783(3) 3713(3) 7432(3) 19.4(12) O0AA 3644(8) 5742(7) 8259(7) 14(3) O2 3762(9) 2063(8) 6209(8) 28(3) O1AA 4596(9) 1503(8) 3840(8) 29(3) O2AA 5985(10) 5715(9) 8548(9) 34(4) C5 2695(13) 6301(12) 1981(12) 20(5) O3AA 1581(10) 5498(8) 5429(8) 28(3) C6 3852(12) 7766(11) 3250(11) 15(4) C7 1847(14) 4122(12) 7720(12) 24(5) C8 5714(13) 5551(11) 7828(12) 18(4) C9 2587(14) 8522(12) 5338(13) 27(5) C (13) 5398(11) 5397(11) 15(4) C (12) 8303(10) 6773(10) 9(4) C (13) 2638(11) 6830(11) 16(4) C (12) 2792(11) 8331(12) 18(4) C (14) 9058(12) 4245(13) 26(5) C (14) 8260(12) 4089(13) 28(5) C (13) 2239(12) 4033(12) 23(5) C (12) 7002(11) 3274(11) 14(4) C (13) 6583(12) 3786(11) 19(5) C (14) 2696(13) 9037(12) 29(5) C20 904(14) 3516(13) 3998(12) 24(5) C (13) 1804(12) 3307(12) 22(5) C22 848(14) 6811(12) 3902(12) 27(5) C (15) 6098(12) 1655(12) 28(5) C (13) 7635(12) 8227(11) 19(5) C25 766(13) 4137(12) 8471(12) 26(5) C (14) 3897(13) 9833(13) 30(5) C (15) 8922(13) 2800(13) 34(5) C (13) 9037(11) 7066(12) 20(5) C (14) 3838(13) 8313(12) 27(5) C (13) 8014(12) 5889(12) 22(5) C31 271(15) 2055(14) 3250(13) 37(6) C32 103(13) 3486(12) 4213(11) 20(5) C (15) 6197(13) 1457(13) 35(6) C (14) 4742(12) 7260(12) 27(5) C (13) 7695(11) 2935(11) 18(5) C (14) 1148(12) 2640(13) 28(5) C (14) 3220(12) 9783(12) 25(5) C38 679(13) 4995(12) 7397(12) 24(5) C39 484(15) 7474(12) 3551(13) 31(5) C (15) 819(13) 4267(14) 34(6) C41 964(13) 2808(12) 3502(11) 19(5) C (15) 9245(13) 5672(13) 36(6) C (18) 9139(15) 8025(15) 53(3) C (15) 9511(14) 6530(13) 35(6) C (13) 4819(12) 3393(12) 21(5) C (14) 5811(12) 811(13) 31(5) C (16) 7124(14) 8035(14) 40(6) C (14) 2720(13) 5976(12) 27(5) C (13) 4005(12) 9143(11) 19(5) C50 954(15) 1076(14) 5887(13) 33(5) S8

9 C (13) 8125(12) 2605(12) 23(5) C (15) 204(14) 3609(13) 37(6) C (14) 2533(13) 5989(13) 31(5) C (14) 1728(12) 5491(13) 30(5) C (14) 9383(13) 3606(12) 29(5) C (14) 3486(12) 8384(12) 26(5) C (18) 8266(16) 8097(16) 53(3) C (15) 363(14) 2798(14) 38(6) C (17) 5899(14) 598(15) 45(6) C (14) 1618(12) 4126(12) 27(5) C61 898(14) 7911(13) 3072(13) 32(5) C (17) 8293(16) 9549(16) 52(7) C63 337(15) 4709(13) 7991(13) 34(5) C (16) 5725(14) 299(15) 45(6) C (17) 8220(15) 8976(14) 46(6) C (18) 7733(16) 9329(16) 58(7) C (19) 7140(16) 8543(16) 57(7) C68-633(17) 2748(14) 3947(14) 43(6) C (15) 1951(13) 7231(14) 34(5) C (18) 7920(16) 8733(15) 53(3) C71-551(18) 2041(16) 3448(15) 53(7) O6 1841(9) 4823(8) 2927(8) 29(3) C (13) 5626(12) 7573(11) 18(4) C73 326(9) 2925(16) 771(11) 53(13) C74 632(11) 2912(16) 1631(11) 40(11) C (12) 2921(11) 2075(8) 38(4) C (9) 2942(15) 1659(10) 22(9) C (11) 2955(15) 799(10) 28(10) C78 974(12) 2947(11) 355(8) 38(4) C74A 730(40) 2250(30) 1540(30) 34(16) C73A 330(40) 2210(30) 640(30) 28(15) C77A 1660(30) 3410(30) 830(30) 16(13) C76A 1990(30) 3450(30) 1700(30) 13(12) Sb1-343(3) -533(2) 979(2) 52.3(9) F1-790(20) -931(19) -209(19) 71(9) F2-1010(20) 290(20) 850(20) 80(10) F3 360(20) -1380(20) 1120(20) 79(9) F4-1350(30) -1220(20) 1060(20) 93(11) F5 70(20) -138(19) 2140(19) 77(9) Table S4. Fractional Atomic Coordinates ( 10 4 ) and Equivalent Isotropic Displacement Parameters (Å ) for Cluster 2. U eq is defined as one third of the trace of the orthogonalized U IJ tensor. Atom x y z U(eq) Pt (3) Pt (5) (5) 553.4(5) 10.0(3) Pt (5) (5) 81.0(5) 10.0(3) Pt (5) (5) 531.7(5) 10.5(3) Pt (5) (5) (5) 11.2(3) Pt (5) (5) (5) 10.6(3) Pt (5) (5) (5) 10.2(3) Pt (5) (5) (5) 12.7(3) Pt (5) (5) (5) 13.7(3) P1 8145(4) 6024(3) 950(4) 15.8(13) P2 6602(3) 5224(3) 3861(3) 14.6(12) P3 5062(3) 7990(3) 5(3) 13.1(12) P4 3575(4) 7291(4) 2929(4) 17.6(13) O1 3740(10) 4189(10) 2321(10) 31(4) O2 6990(10) 7596(10) 830(9) 24(4) C1 8709(14) 5070(14) 893(14) 20(5) C2 3525(14) 8504(13) 2182(13) 18(5) C3 8413(15) 6520(14) 278(15) 25(5) C4 2724(13) 6645(13) 3013(13) 17(5) S9

10 C5 9126(13) 4718(13) 305(13) 14(5) C6 6525(14) 6968(14) 587(13) 17(5) C7 8707(13) 4700(13) 1471(13) 14(5) C8 3031(13) 7995(13) 2381(13) 18(5) C9 2066(15) 6135(14) 2278(15) 26(5) C (15) 8659(14) 4452(14) 22(5) C (16) 8870(15) 5177(15) 30(6) C9AA 9112(14) 3964(14) 1473(14) 22(5) C (13) 6779(13) 2044(13) 16(5) C0BA 1785(18) 8678(17) 1830(17) 41(7) C7AA 8757(17) 7880(16) 3346(16) 36(6) C1BA 5997(15) 9444(15) 2591(16) 30(6) C (14) 8110(14) -246(15) 25(5) C (16) 6891(16) 2388(16) 36(6) C (16) 7980(16) 3656(17) 35(6) C (14) 4209(13) 3849(13) 18(5) C (15) 8253(15) 4392(15) 26(5) C2BA 9526(15) 3970(15) 305(15) 27(5) C8AA 3758(14) 8258(13) -1366(13) 18(5) C4AA 4105(16) 9316(16) 5227(15) 32(6) C5AA 9553(16) 3627(16) 912(15) 34(6) C6AA 4983(16) 9413(16) 5597(16) 34(6) C (13) 5140(13) 3886(13) 16(5) C (16) 9117(16) 1831(16) 35(6) C (16) 5571(15) 3067(15) 32(6) C (17) 6469(17) -1154(17) 39(6) C (14) 8780(14) 1800(13) 20(5) C (16) 6610(16) 3781(16) 32(6) C0AA 8865(15) 5718(15) 3631(14) 25(5) C 8054(14) 5729(14) 3603(14) 23(5) C3BA 5303(13) 8877(13) 1054(13) 16(5) C (15) 7349(15) 638(16) 28(6) C (15) 8106(15) 4006(15) 26(6) C (18) 7507(17) 3218(17) 41(7) C (15) 10241(15) 2616(15) 28(6) C (16) 8099(16) 2232(16) 34(6) C (16) 6077(16) -609(15) 31(6) C (17) 5601(16) 2311(17) 36(6) C (14) 4386(14) 1877(14) 20(5) C (16) 8650(15) -1183(15) 31(6) C (16) 8282(15) -626(15) 30(6) C (17) 7263(15) 2518(16) 33(6) C (16) 6066(16) 3801(17) 36(6) C (15) 9043(15) -22(15) 27(6) C (15) 4226(16) 4203(15) 31(6) C1AA 9050(16) 4539(16) 4160(15) 32(6) C (14) 8126(13) -594(13) 19(5) C2AA 9381(15) 5114(14) 3890(14) 26(5) C (13) 8286(13) -462(13) 15(5) C (14) 3388(14) 3452(14) 22(5) C (14) 7929(14) -1642(15) 23(5) C (15) 8415(14) -1744(15) 26(5) C3AA 8226(14) 4595(14) 4203(14) 21(5) C (17) 9181(17) 1655(17) 39(7) C (14) 7724(14) -1275(13) 18(5) C (14) 9202(14) -379(14) 23(5) C (14) 2660(14) 3464(14) 22(5) C (15) 8398(14) -1421(15) 27(6) C (19) 7270(20) -780(20) 55(8) C (15) 9659(14) 1105(15) 27(6) C (18) 7706(18) 49(17) 44(7) C (14) 10331(15) 1910(14) 23(5) C (15) 2676(16) 3828(15) 30(6) C (16) 3435(15) 4169(15) 29(6) O3 4793(9) 6163(9) 3903(9) 24(4) C (13) 6113(12) 3272(13) 12(5) C (10) 5806(7) 5651(8) 32(6) S10

11 C (9) 6043(7) 4946(7) 11(5) C (9) 6920(8) 5066(7) 19(5) C (10) 7561(6) 5890(8) 27(6) C (10) 7324(8) 6595(6) 34(6) C (11) 6446(9) 6476(7) 38(6) O6 2361(9) 6963(9) 368(9) 18(3) O7 7482(9) 3647(9) 2030(9) 23(4) C (11) 4022(11) 1723(11) 3(4) C (12) 6601(12) 405(12) 9(4) O8 6527(10) 7765(10) 3262(10) 28(4) C (12) 7202(12) 2623(12) 7(4) Sb1 8444(2) 9790(2) 5588(2) 38.8(9) F1 9334(18) 9881(19) 5216(18) 45(5) F2 7694(19) 9543(19) 4499(19) 46(5) F3 7550(20) 9700(20) 5960(20) 57(6) F4 8480(20) 8580(20) 5290(20) 54(6) F5 8344(18) 10920(19) 5790(20) 48(5) F6 9200(20) 10100(20) 6680(20) 59(6) Sb2-46(4) 9526(4) -733(4) 81.1(15) F7 960(30) 10290(30) 220(30) 103(14) F8-650(60) 8930(60) -1830(60) 230(40) F9 320(40) 9450(40) 680(40) 129(18) O5 8590(20) 10953(17) 3245(19) 38(8) C (30) 12290(30) 4330(30) 40(13) C (30) 11360(30) 4030(30) 55(15) C (30) 10010(30) 2920(30) 59(15) C (30) 9630(30) 2120(30) 42(13) 3.4 Additional Refinement Details for Each Cluster. Cluster 1: Number of restraints: 165, number of constraints: unknown. Details: 1. Fixed Uiso At 1.2 times of: All C(H) groups 2. Restrained planarity C76, C75, C77, C78, C73, and C74 with σ = Uiso/Uaniso restraints and constraints Uiso(C4) = Uiso(C2) Uiso(C78) = Uiso(C75) Uiso(C2) = Uiso(C57) Uiso(C3) = Uiso(C4) Uiso(C57) = Uiso(C3) Uiso(C43) = Uiso(C4) Uiso(C57) = Uiso(C3) Uiso(C57) = Uiso(C70) 4. Rigid body (RIGU) restraints All non-hydrogen atoms with σ for 1 2 distances of and σ for 1 3 distances of Others Sof(C74A) = Sof(C73A) = Sof(C77A) = Sof(C76A) = 1-FVAR(1) Sof(C73) = Sof(C74) = Sof(C76) = Sof(C77) = FVAR(1) Fixed Sof: Sb1(0.5), F1(0.5), F2(0.5), F3(0.5), F4(0.5), F5(0.5), F6(0.5) 6.a Aromatic/amide H refined with riding coordinates: C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C13(H13), C14(H14), C15(H15), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), S11

12 C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71) 6.b Fitted hexagon refined as a free rotating group: C73(C74,C75,C76,C77,C78) Cluster 2: Number of restraints: 179, number of constraints: unknown. Details: 1. Fixed Uiso At 1.2 times of: All C(H) groups 2. Restrained distances C12 C14 C15 C16 with σ = 0.02 O5 C14 O5 C15 with σ = 0.02 C12 O5 O5 C16 with σ = Restrained planarity C12, C14, C15, and C16 with σ = Uiso/Uaniso restraints and constraints All non-hydrogen atoms have similar U: within 1.7A with σ = 0.04 and σ for terminal atoms of Rigid body (RIGU) restraints All non-hydrogen atoms with σ for 1 2 distances of and σ for 1 3 distances of Others Fixed Sof: Sb1(0.5), F1(0.5), F2(0.5), F3(0.5), F4(0.5), F5(0.5), F6(0.5), Sb2(0.5) F7(0.5), F8(0.5), F9(0.5), O5(0.5), C12(0.5), C14(0.5), C15(0.5), C16(0.5) 7.a Aromatic/amide H refined with riding coordinates: C2(H2), C5(H5), C7(H7), C9(H9), C10(H10), C11(H11), C9AA(H9AA), C0BA(H0BA), C7AA(H7AA), C1BA(H1BA), C17(H17), C18(H18), C19(H19), C21(H21), C2BA(H2BA), C8AA(H8AA), C4AA(H4AA), C5AA(H5AA), C6AA(H6AA), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C0AA(H0AA), C(H), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C1AA(H1AA), C2AA(H2AA), C54(H54), C55(H55), C56(H56), C3AA(H3AA), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C70(H70), C72(H72), C73(H73), C74(H74), C75(H75) 7.b Fitted hexagon refined as a free rotating group: C70(C71,C72,C73,C74,C75) 4. References (1) Edwards, H. G. M.; Johnson, A. F.; Lewis, I. R. A Vibrational Spectroscopic Study of Tris Triphenyl Phosphine Rhodium (I) Chloride. Spectrochimica Acta A. 1993, 49A, (2) Roth, J. D.; Lewis, G. J.; Safford, L. K.; Jiang, X.; Dahl, L. F.; Weaver, M. J. Exploration of the Ionizable Metal Cluster Electrode Surface Analogy: Infrared Spectroelectrochemistry of [Pt 24 (CO) 30 ] n, [Pt 26 (CO) 32 ] n, and [Pt 38 (CO) 44 ] n (n = 0 to 10) and Comparisons with Potential-Dependent Spectra of CO Adlayers on Platinum Surfaces. J. Am. Chem. Soc. 1992, 114, (3) Sheldrick, G. M. SHELXT Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr. Sect. A: Found. Adv. 2015, A71, 3 8. (4) Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. C: Struct. Chem. 2015, C71, 3 8. (5) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: A Complete Structure Solution, Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42, (6) Spek, A. L. PLATON SQUEEZE: A Tool for the Calculation of the Disordered Solvent Contribution to the Calculated Structure Factors. Acta Crystallogr. Sect. C: Struct. Chem. 2015, C71, (7) Guzei, I. A. An Idealized Molecular Geometry Library for Refinement of Poorly Behaved Molecular Fragments with Constraints. J. Appl. Crystallogr. 2014, 47, S12

Magnetic Ordering in TCNQ-Based Metal-Organic Frameworks With Host-Guest Interactions

Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers. This journal is the Partner Organisations 215 Magnetic Ordering in TCNQ-Based Metal-Organic Frameworks With Host-Guest Interactions