APPENDIX

X-Ray measurements and structure elucidations were done at the University of Konstanz (Dr. T. Huhn and B. Weibert) and at SSI "Institute for Single Crystals", Kharkiv, Ukraine (Prof. Dr.

O. Shishkin).

Description of quantum yields determination is given in “Synthesis and Photoswitching Studies of Difurylperfluorocyclopentenes with Extended π-Systems”, D. Sysoiev, A. Fedoseev, Y.

Kim, T. Exner, J. Boneberg, T. Huhn, P. Leiderer, E. Scheer, U. Groth and U. Steiner, Chem. Eur.

J., 17 (24), 2011, pp. 6663–6672.

Investigation of the photokinetic behaviour of synthesized diarylethenes was done in collaboration with A. Fedoseev and T. Yushchenko under supervision of Prof. Dr. U. Steiner at the University of Konstanz.

Appendix

O N

N O

CF₂ F₂ F₂C C

Crystal data and structure refinement for 23.

Empirical formula C15 H12 F6 N2 O2

Formula weight 366.27

Temperature 100(2) K

Wavelength 0.71073 A

Crystal system monoclinic

Space group P2(1)/c

Unit cell dimensions a = 14.6261(9) A alpha = 90 deg.

b = 13.7893(9) A beta = 90.866(5) deg.

c = 7.8855(5) A gamma = 90 deg.

Volume 1590.20(17) A^3

Z 4 Calculated density 1.530 Mg/m^3

Absorption coefficient 0.149 mm^-1

F(000) 744

Crystal size 0.20 x 0.10 x 0.02 mm

Theta range for data collection 2.95 to 30.00 deg.

Limiting indices -18<=h<=20, -18<=k<=19, -11<=l<=10 Reflections collected / unique 15649 / 4597 [R(int) = 0.0437]

Completeness to theta = 30.00 98.9 %

Max. and min. transmission 0.9970 and 0.9708

Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 4597 / 20 / 302

Goodness-of-fit on F^2 1.052

Final R indices [I>2sigma(I)] R1 = 0.0659, wR2 = 0.1624

Appendix

Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for 23. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

x y z U(eq) O(1) 2213(2) 7683(1) 3995(2) 65(1) O(2) 4717(2) 3849(2) 5000(3) 72(1) N(1) 3020(1) 7552(1) 3019(2) 40(1) N(2) 4221(2) 4245(1) 6346(3) 49(1) C(1) 2528(2) 4352(1) 2931(3) 44(1) C(2A) 1903(3) 3498(3) 2588(6) 64(2) C(4A) 1061(4) 4924(3) 1913(8) 61(4) F(1A) 2345(5) 2820(5) 1694(8) 85(2) F(2A) 1439(3) 3066(3) 3840(5) 73(1) F(3A) 322(2) 3449(3) 1379(6) 62(1) F(4A) 1380(3) 3953(3) -295(4) 60(1) F(5A) 810(3) 5607(2) 703(5) 48(1) F(6A) 388(5) 5046(5) 3079(8) 61(2) C(2B) 2217(3) 3518(2) 1790(4) 45(1) C(4B) 1207(4) 4939(3) 1548(6) 52(2) F(1B) 2329(3) 2645(2) 2549(5) 65(1) F(2B) 2743(2) 3424(2) 357(3) 55(1) F(3B) 1005(2) 3467(3) -186(4) 76(1) F(4B) 714(2) 3355(2) 2502(4) 76(1) F(5B) 413(3) 5171(4) 2221(6) 77(2) F(6B) 1303(2) 5297(2) -17(3) 63(1) C(3) 1192(2) 3843(2) 1345(3) 58(1) C(5) 2009(1) 5150(2) 2692(2) 35(1) C(6) 2251(1) 6147(2) 3117(2) 32(1) C(7) 1774(2) 6856(2) 4007(3) 46(1) C(8) 3020(1) 6637(2) 2542(2) 36(1) C(9) 3344(2) 4246(1) 3991(3) 40(1) C(10) 4190(2) 3851(2) 3616(3) 54(1) C(11) 3416(2) 4478(2) 5719(3) 43(1) C(12) 917(2) 6808(3) 4984(4) 74(1) C(13) 3785(2) 6306(2) 1484(3) 47(1) C(14) 2737(2) 4916(2) 6867(3) 56(1) C(15) 4593(3) 3485(3) 2019(4) 83(1)

Appendix

Bond lengths [A] and angles [deg] for 23.

O(1)-C(7) 1.310(3) C(5)-C(1)-C(9) 128.13(18) F(3B)-C(3)-C(4B) 118.9(3) O(1)-N(1) 1.431(3) C(5)-C(1)-C(2A) 105.9(3) F(4B)-C(3)-C(4B) 115.8(3) O(2)-C(10) 1.327(3) C(9)-C(1)-C(2A) 120.9(2) F(3A)-C(3)-C(4B) 113.6(3) O(2)-N(2) 1.404(3) C(5)-C(1)-C(2B) 111.8(2) C(2A)-C(3)-C(4B) 103.8(3) N(1)-C(8) 1.316(3) C(9)-C(1)-C(2B) 119.9(2) F(4A)-C(3)-C(4A) 101.3(3) N(2)-C(11) 1.310(3) C(2A)-C(1)-C(2B) 30.0(2) F(3B)-C(3)-C(4A) 127.0(3) C(1)-C(5) 1.347(3) F(1A)-C(2A)-F(2A) 109.2(5) F(4B)-C(3)-C(4A) 102.4(3) C(1)-C(9) 1.454(3) F(1A)-C(2A)-C(3) 102.2(4) F(3A)-C(3)-C(4A) 104.5(3) C(1)-C(2A) 1.512(4) F(2A)-C(2A)-C(3) 105.6(4) C(2A)-C(3)-C(4A) 101.6(3) C(1)-C(2B) 1.525(3) F(1A)-C(2A)-C(1) 110.0(5) C(4B)-C(3)-C(4A) 13.3(4) C(2A)-F(1A) 1.342(5) F(2A)-C(2A)-C(1) 121.6(4) F(4A)-C(3)-C(2B) 92.2(3) C(2A)-F(2A) 1.345(4) C(3)-C(2A)-C(1) 106.3(3) F(3B)-C(3)-C(2B) 105.5(2) C(2A)-C(3) 1.496(4) F(6A)-C(4A)-F(5A) 101.1(4) F(4B)-C(3)-C(2B) 101.9(3) C(4A)-F(6A) 1.368(5) F(6A)-C(4A)-C(5) 111.1(5) F(3A)-C(3)-C(2B) 138.1(3) C(4A)-F(5A) 1.386(5) F(5A)-C(4A)-C(5) 111.4(4) C(2A)-C(3)-C(2B) 29.2(2) C(4A)-C(5) 1.540(5) F(6A)-C(4A)-C(3) 113.6(5) C(4B)-C(3)-C(2B) 104.1(2) C(4A)-C(3) 1.569(5) F(5A)-C(4A)-C(3) 118.8(4) C(4A)-C(3)-C(2B) 108.8(2) F(3A)-C(3) 1.384(4) C(5)-C(4A)-C(3) 101.1(3) C(1)-C(5)-C(6) 127.14(19) F(4A)-C(3) 1.334(4) F(1B)-C(2B)-F(2B) 102.3(3) C(1)-C(5)-C(4B) 111.1(2) C(2B)-F(1B) 1.353(4) F(1B)-C(2B)-C(1) 112.1(3) C(6)-C(5)-C(4B) 120.4(2) C(2B)-F(2B) 1.382(4) F(2B)-C(2B)-C(1) 112.9(3) C(1)-C(5)-C(4A) 113.1(2) C(2B)-C(3) 1.599(4) F(1B)-C(2B)-C(3) 116.9(3) C(6)-C(5)-C(4A) 119.7(2) C(4B)-F(5B) 1.324(4) F(2B)-C(2B)-C(3) 112.2(2) C(4B)-C(5)-C(4A) 13.6(4) C(4B)-F(6B) 1.338(4) C(1)-C(2B)-C(3) 100.9(2) C(8)-C(6)-C(7) 103.6(2) C(4B)-C(5) 1.498(4) F(5B)-C(4B)-F(6B) 112.6(4) C(8)-C(6)-C(5) 125.22(18) C(4B)-C(3) 1.519(4) F(5B)-C(4B)-C(5) 113.3(4) C(7)-C(6)-C(5) 130.9(2) F(3B)-C(3) 1.338(3) F(6B)-C(4B)-C(5) 113.1(4) O(1)-C(7)-C(6) 111.0(2) F(4B)-C(3) 1.339(3) F(5B)-C(4B)-C(3) 105.7(4) O(1)-C(7)-C(12) 117.5(2) C(5)-C(6) 1.457(3) F(6B)-C(4B)-C(3) 105.7(3) C(6)-C(7)-C(12) 131.5(3) C(6)-C(8) 1.394(3) C(5)-C(4B)-C(3) 105.5(3) N(1)-C(8)-C(6) 111.59(19) C(6)-C(7) 1.397(3) F(4A)-C(3)-F(3B) 38.0(2) N(1)-C(8)-C(13) 117.4(2) C(7)-C(12) 1.483(4) F(4A)-C(3)-F(4B) 146.6(3) C(6)-C(8)-C(13) 131.0(2) C(8)-C(13) 1.478(3) F(3B)-C(3)-F(4B) 108.6(3) C(10)-C(9)-C(11) 104.0(2) C(9)-C(10) 1.389(4) F(4A)-C(3)-F(3A) 105.5(3) C(10)-C(9)-C(1) 130.0(2) C(9)-C(11) 1.402(3) F(3B)-C(3)-F(3A) 72.0(3) C(11)-C(9)-C(1) 125.8(2) C(10)-C(15) 1.486(4) F(4B)-C(3)-F(3A) 45.6(2) O(2)-C(10)-C(9) 109.5(2) C(11)-C(14) 1.483(3) F(4A)-C(3)-C(2A) 121.3(3) O(2)-C(10)-C(15) 117.7(3) C(7)-O(1)-N(1) 107.56(16) F(3B)-C(3)-C(2A) 126.8(3) C(9)-C(10)-C(15) 132.8(3)

Appendix

Anisotropic displacement parameters (A^2 x 10^3) for 23. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]

U11 U22 U33 U23 U13 U12 O(1) 69(1) 53(1) 72(1) -20(1) -21(1) 14(1) O(2) 61(1) 66(1) 90(2) 21(1) -13(1) 11(1) N(1) 40(1) 34(1) 45(1) 2(1) -13(1) -5(1) N(2) 48(1) 47(1) 51(1) 7(1) -14(1) 4(1) C(1) 59(2) 33(1) 38(1) -1(1) -9(1) -6(1)

C(2A) 106(7) 43(4) 42(4) -9(3) -14(4) 14(4)

C(4A) 88(10) 52(6) 43(4) 34(4) -33(5) -38(6) F(1A) 90(4) 60(4) 104(5) -32(4) -43(5) 35(4) F(2A) 89(3) 47(2) 82(3) 33(2) -32(2) -24(2) F(3A) 64(3) 42(2) 78(3) -1(2) -29(2) -15(2) F(4A) 64(3) 65(3) 51(2) -15(2) -12(2) -4(2) F(5A) 48(2) 41(2) 56(2) 18(2) -22(2) -7(2) F(6A) 39(3) 45(2) 98(5) -7(3) -23(3) -7(2) C(2B) 80(3) 29(2) 26(2) -4(2) -5(2) -13(2)

C(4B) 37(3) 60(4) 57(3) 8(3) -20(3) -15(3)

F(1B) 96(3) 29(1) 71(2) -3(2) 4(2) -20(2) F(2B) 61(2) 57(1) 46(1) -24(1) 10(1) -6(1) F(3B) 64(2) 96(3) 67(2) -36(2) -16(2) -22(2) F(4B) 61(2) 75(2) 92(2) -10(2) 29(2) -34(2) F(5B) 36(2) 88(3) 104(4) -30(3) -33(3) 10(2)

F(6B) 63(2) 80(2) 44(2) 5(1) -22(1) -18(2)

C(3) 58(2) 67(2) 48(1) -10(1) -3(1) -28(1) C(5) 33(1) 40(1) 31(1) 3(1) -4(1) -7(1) C(6) 28(1) 35(1) 32(1) -1(1) -5(1) 3(1) C(7) 35(1) 61(2) 42(1) -12(1) -8(1) 12(1) C(8) 32(1) 41(1) 34(1) 5(1) -10(1) -1(1) C(9) 50(1) 30(1) 39(1) 4(1) -5(1) 3(1) C(10) 65(2) 43(1) 54(1) 6(1) 2(1) 13(1) C(11) 51(2) 36(1) 42(1) 7(1) -11(1) -1(1) C(12) 50(2) 107(3) 65(2) -27(2) 9(1) 19(2) C(13) 35(1) 63(2) 42(1) 13(1) 0(1) -3(1) C(14) 73(2) 57(2) 37(1) 1(1) -6(1) 8(1) C(15) 94(3) 79(2) 78(2) 1(2) 20(2) 36(2)

Appendix

Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for 23.

_ x y z U(eq)

H(12A) 854 7399 5662 111

H(12B) 936 6242 5736 111

H(12C) 394 6750 4198 111

H(13A) 4033 6858 858 70

H(13B) 3564 5814 680 70

H(13C) 4266 6026 2212 70

H(14A) 2847 4682 8026 84

H(14B) 2119 4730 6494 84

H(14C) 2794 5623 6841 84

H(15A) 5259 3448 2152 125

H(15B) 4436 3928 1087 125

H(15C) 4348 2839 1766 125

Table 6. Torsion angles [deg] for 23.

C(7)-O(1)-N(1)-C(8) -1.5(2) F(2B)-C(2B)-C(3)-F(4A) -5.4(3) C(10)-O(2)-N(2)-C(11) -0.5(3) C(1)-C(2B)-C(3)-F(4A) 115.0(3) C(5)-C(1)-C(2A)-F(1A) 138.4(4) F(1B)-C(2B)-C(3)-F(3B) -87.0(4) C(9)-C(1)-C(2A)-F(1A) -65.0(5) F(2B)-C(2B)-C(3)-F(3B) 30.7(3) C(2B)-C(1)-C(2A)-F(1A) 32.2(4) C(1)-C(2B)-C(3)-F(3B) 151.2(3) C(5)-C(1)-C(2A)-F(2A) -92.2(4) F(1B)-C(2B)-C(3)-F(4B) 26.4(4) C(9)-C(1)-C(2A)-F(2A) 64.4(5) F(2B)-C(2B)-C(3)-F(4B) 144.1(3) C(2B)-C(1)-C(2A)-F(2A) 161.6(8) C(1)-C(2B)-C(3)-F(4B) -95.5(2) C(5)-C(1)-C(2A)-C(3) 28.4(4) F(1B)-C(2B)-C(3)-F(3A) -6.9(6) C(9)-C(1)-C(2A)-C(3) -175.0(2) F(2B)-C(2B)-C(3)-F(3A) 110.9(4) C(2B)-C(1)-C(2A)-C(3) -77.8(4) C(1)-C(2B)-C(3)-F(3A) -128.7(4) C(5)-C(1)-C(2B)-F(1B) -145.8(3) F(1B)-C(2B)-C(3)-C(2A) 54.0(5) C(9)-C(1)-C(2B)-F(1B) 39.1(4) F(2B)-C(2B)-C(3)-C(2A) 171.7(6) C(2A)-C(1)-C(2B)-F(1B) -61.8(5) C(1)-C(2B)-C(3)-C(2A) -67.8(4) C(5)-C(1)-C(2B)-F(2B) 99.2(3) F(1B)-C(2B)-C(3)-C(4B) 147.1(3) C(9)-C(1)-C(2B)-F(2B) -75.8(3) F(2B)-C(2B)-C(3)-C(4B) -95.1(3) C(2A)-C(1)-C(2B)-F(2B) -176.7(6) C(1)-C(2B)-C(3)-C(4B) 25.3(3) C(5)-C(1)-C(2B)-C(3) -20.7(3) F(1B)-C(2B)-C(3)-C(4A) 134.1(4) C(9)-C(1)-C(2B)-C(3) 164.2(2) F(2B)-C(2B)-C(3)-C(4A) -108.2(3) C(2A)-C(1)-C(2B)-C(3) 63.4(4) C(1)-C(2B)-C(3)-C(4A) 12.2(4) F(1A)-C(2A)-C(3)-F(4A) -39.1(6) C(9)-C(1)-C(5)-C(6) 15.4(4) F(2A)-C(2A)-C(3)-F(4A) -153.3(4) C(2A)-C(1)-C(5)-C(6) 169.7(3)

Appendix

F(2A)-C(2A)-C(3)-F(3B) -107.4(4) C(2A)-C(1)-C(5)-C(4B) -23.6(4) C(1)-C(2A)-C(3)-F(3B) 122.1(4) C(2B)-C(1)-C(5)-C(4B) 7.5(3) F(1A)-C(2A)-C(3)-F(4B) 109.7(5) C(9)-C(1)-C(5)-C(4A) -163.4(3) F(2A)-C(2A)-C(3)-F(4B) -4.5(3) C(2A)-C(1)-C(5)-C(4A) -9.1(4) C(1)-C(2A)-C(3)-F(4B) -134.9(4) C(2B)-C(1)-C(5)-C(4A) 22.0(4) F(1A)-C(2A)-C(3)-F(3A) 95.5(5) F(5B)-C(4B)-C(5)-C(1) 125.3(4) F(2A)-C(2A)-C(3)-F(3A) -18.7(5) F(6B)-C(4B)-C(5)-C(1) -105.0(4) C(1)-C(2A)-C(3)-F(3A) -149.1(3) C(3)-C(4B)-C(5)-C(1) 10.1(4) F(1A)-C(2A)-C(3)-C(4B) -136.7(5) F(5B)-C(4B)-C(5)-C(6) -67.0(5) F(2A)-C(2A)-C(3)-C(4B) 109.1(4) F(6B)-C(4B)-C(5)-C(6) 62.7(5) C(1)-C(2A)-C(3)-C(4B) -21.3(4) C(3)-C(4B)-C(5)-C(6) 177.8(2) F(1A)-C(2A)-C(3)-C(4A) -150.2(5) F(5B)-C(4B)-C(5)-C(4A) 24.0(10) F(2A)-C(2A)-C(3)-C(4A) 95.6(4) F(6B)-C(4B)-C(5)-C(4A) 153.7(13) C(1)-C(2A)-C(3)-C(4A) -34.8(4) C(3)-C(4B)-C(5)-C(4A) -91.2(11) F(1A)-C(2A)-C(3)-C(2B) -42.4(5) F(6A)-C(4A)-C(5)-C(1) 108.7(4) F(2A)-C(2A)-C(3)-C(2B) -156.6(6) F(5A)-C(4A)-C(5)-C(1) -139.4(4) C(1)-C(2A)-C(3)-C(2B) 72.9(4) C(3)-C(4A)-C(5)-C(1) -12.2(4) F(5B)-C(4B)-C(3)-F(4A) 125.5(4) F(6A)-C(4A)-C(5)-C(6) -70.2(5) F(6B)-C(4B)-C(3)-F(4A) 5.9(4) F(5A)-C(4A)-C(5)-C(6) 41.8(6) C(5)-C(4B)-C(3)-F(4A) -114.2(4) C(3)-C(4A)-C(5)-C(6) 168.9(2) F(5B)-C(4B)-C(3)-F(3B) 100.6(4) F(6A)-C(4A)-C(5)-C(4B) -167.2(13) F(6B)-C(4B)-C(3)-F(3B) -19.0(5) F(5A)-C(4A)-C(5)-C(4B) -55.2(11) C(5)-C(4B)-C(3)-F(3B) -139.1(3) C(3)-C(4A)-C(5)-C(4B) 71.9(11) F(5B)-C(4B)-C(3)-F(4B) -31.4(4) C(1)-C(5)-C(6)-C(8) 56.2(3)

F(6B)-C(4B)-C(3)-F(4B) -151.1(3) C(4B)-C(5)-C(6)-C(8) -109.4(3) C(5)-C(4B)-C(3)-F(4B) 88.9(4) C(4A)-C(5)-C(6)-C(8) -125.1(4) F(5B)-C(4B)-C(3)-F(3A) 19.0(4) C(1)-C(5)-C(6)-C(7) -130.4(3) F(6B)-C(4B)-C(3)-F(3A) -100.7(4) C(4B)-C(5)-C(6)-C(7) 64.0(4)

C(5)-C(4B)-C(3)-F(3A) 139.3(3) C(4A)-C(5)-C(6)-C(7) 48.3(4) F(5B)-C(4B)-C(3)-C(2A) -112.3(4) N(1)-O(1)-C(7)-C(6) 1.4(2)

F(6B)-C(4B)-C(3)-C(2A) 128.0(4) N(1)-O(1)-C(7)-C(12) 178.6(2) C(5)-C(4B)-C(3)-C(2A) 8.0(4) C(8)-C(6)-C(7)-O(1) -0.9(2) F(5B)-C(4B)-C(3)-C(4A) -30.1(10) C(5)-C(6)-C(7)-O(1) -175.3(2) F(6B)-C(4B)-C(3)-C(4A) -149.7(13) C(8)-C(6)-C(7)-C(12) -177.5(3) C(5)-C(4B)-C(3)-C(4A) 90.2(11) C(5)-C(6)-C(7)-C(12) 8.0(4) F(5B)-C(4B)-C(3)-C(2B) -142.4(3) O(1)-N(1)-C(8)-C(6) 0.9(2)

F(6B)-C(4B)-C(3)-C(2B) 98.0(3) O(1)-N(1)-C(8)-C(13) 179.27(17) C(5)-C(4B)-C(3)-C(2B) -22.1(4) C(7)-C(6)-C(8)-N(1) -0.1(2)

F(6A)-C(4A)-C(3)-F(4A) 143.2(5) C(5)-C(6)-C(8)-N(1) 174.77(19) F(5A)-C(4A)-C(3)-F(4A) 24.5(5) C(7)-C(6)-C(8)-C(13) -178.1(2) C(5)-C(4A)-C(3)-F(4A) -97.7(4) C(5)-C(6)-C(8)-C(13) -3.3(3) F(6A)-C(4A)-C(3)-F(3B) 112.0(5) C(5)-C(1)-C(9)-C(10) -131.1(3)

Appendix

F(5A)-C(4A)-C(3)-F(3B) -6.8(7) C(2A)-C(1)-C(9)-C(10) 78.0(4) C(5)-C(4A)-C(3)-F(3B) -129.0(3) C(2B)-C(1)-C(9)-C(10) 43.2(4) F(6A)-C(4A)-C(3)-F(4B) -13.1(5) C(5)-C(1)-C(9)-C(11) 53.7(3) F(5A)-C(4A)-C(3)-F(4B) -131.8(5) C(2A)-C(1)-C(9)-C(11) -97.2(3) C(5)-C(4A)-C(3)-F(4B) 106.0(4) C(2B)-C(1)-C(9)-C(11) -132.1(3) F(6A)-C(4A)-C(3)-F(3A) 33.8(5) N(2)-O(2)-C(10)-C(9) 0.4(3) F(5A)-C(4A)-C(3)-F(3A) -85.0(5) N(2)-O(2)-C(10)-C(15) 178.3(2) C(5)-C(4A)-C(3)-F(3A) 152.9(3) C(11)-C(9)-C(10)-O(2) 0.0(3) F(6A)-C(4A)-C(3)-C(2A) -91.1(5) C(1)-C(9)-C(10)-O(2) -176.1(2) F(5A)-C(4A)-C(3)-C(2A) 150.1(5) C(11)-C(9)-C(10)-C(15) -177.6(3) C(5)-C(4A)-C(3)-C(2A) 28.0(4) C(1)-C(9)-C(10)-C(15) 6.4(5) F(6A)-C(4A)-C(3)-C(4B) 168.1(13) O(2)-N(2)-C(11)-C(9) 0.5(3) F(5A)-C(4A)-C(3)-C(4B) 49.4(10) O(2)-N(2)-C(11)-C(14) 179.8(2) C(5)-C(4A)-C(3)-C(4B) -72.8(11) C(10)-C(9)-C(11)-N(2) -0.3(3) F(6A)-C(4A)-C(3)-C(2B) -120.5(4) C(1)-C(9)-C(11)-N(2) 175.9(2) F(5A)-C(4A)-C(3)-C(2B) 120.8(4) C(10)-C(9)-C(11)-C(14) -179.4(2) C(5)-C(4A)-C(3)-C(2B) -1.4(4) C(1)-C(9)-C(11)-C(14) -3.2(4) F(1B)-C(2B)-C(3)-F(4A) -123.2(4)

Appendix

O O

CF₂ F₂C

O O

Crystal data and structure refinement for 28.

Empirical formula C16 H10 F4 O4

Formula weight 342.24

Temperature 100(2) K

Wavelength 0.71073 A

Crystal system triclinic

Space group P-1

Unit cell dimensions a = 7.7858(17) A alpha = 91.76(2) deg.

b = 11.482(3) A beta = 90.552(18) deg.

c = 16.563(4) A gamma = 106.03(2) deg.

Volume 1422.2(6) A^3

Z 4 Calculated density 1.598 Mg/m^3

Absorption coefficient 0.148 mm^-1

F(000) 696

Crystal size 0.20 x 0.02 x 0.02 mm

Theta range for data collection 2.97 to 25.00 deg.

Limiting indices -9<=h<=7, -13<=k<=9, -19<=l<=15 Reflections collected / unique 7679 / 4910 [R(int) = 0.1024]

Completeness to theta = 30.00 97.8 %

Max. and min. transmission 0.9970 and 0.9710

Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 4910 / 0 / 437

Goodness-of-fit on F^2 0.894

Final R indices [I>2sigma(I)] R1 = 0.0948, wR2 = 0.1810 R indices (all data) R1 = 0.2562, wR2 = 0.2362 Largest diff. peak and hole 0.424 and -0.296 e.A^-3

Appendix

Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for 28. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

_ x y z U(eq)

F(1A) 2243(5) 4776(4) 410(3) 50(1)

F(2A) 4687(5) 6229(4) 264(3) 56(1)

F(3A) 3872(6) 7416(4) 1552(3) 56(1)

F(4A) 1466(6) 5978(5) 1706(3) 60(1)

O(1A) -956(6) 9337(4) 1391(3) 40(1)

O(2A) -4055(7) 9996(5) 974(3) 54(2)

O(3A) 1934(6) 6309(5) -2285(3) 45(1)

O(4A) 1379(7) 7718(5) -3597(4) 56(2)

C(1A) 1873(9) 6694(7) -90(5) 36(2)

C(2A) 2925(9) 5999(7) 393(5) 37(2)

C(3A) 2397(10) 6651(8) 1130(5) 46(2)

C(4A) 1441(9) 7254(7) 562(4) 37(2)

C(5A) 274(9) 8031(7) 731(5) 40(2)

C(6A) -1195(9) 8159(7) 253(5) 42(2)

C(7A) -1899(10) 8933(7) 676(5) 45(2)

C(8A) 406(10) 8771(8) 1408(5) 51(2)

C(9A) 1567(10) 9030(8) 2137(5) 53(2)

C(10A) -3517(10) 9347(7) 506(5) 48(2)

C(11A) 1669(9) 6693(7) -959(5) 41(2) C(12A) 1075(9) 7559(7) -1415(5) 41(2) C(13A) 1245(9) 7306(7) -2196(5) 39(2) C(14A) 2190(9) 5983(7) -1526(5) 40(2) C(15A) 2956(10) 4928(8) -1492(5) 52(2) C(16A) 949(9) 7907(7) -2908(5) 42(2)

F(1B) 8911(6) 7376(4) 3564(3) 60(1)

F(2B) 6473(6) 5943(4) 3332(3) 58(1)

F(3B) 7241(5) 4763(4) 4597(3) 47(1)

F(4B) 9699(5) 6206(4) 4819(3) 52(1)

O(1B) 6899(6) 6346(5) 7332(3) 45(1)

O(2B) 6235(7) 7699(5) 8686(3) 55(2)

O(3B) 4125(6) 9334(5) 3736(3) 43(1)

O(4B) 1099(7) 10069(5) 4124(3) 53(2)

C(1B) 6490(9) 7240(7) 4515(5) 41(2)

C(2B) 7470(11) 6652(9) 3921(5) 52(2)

C(3B) 7921(9) 5990(8) 4650(5) 41(2)

C(4B) 6929(9) 6700(7) 5174(5) 40(2)

Appendix

C(7B) 6222(9) 7357(7) 7267(5) 41(2)

C(8B) 7175(9) 5993(8) 6569(5) 40(2)

C(9B) 7950(11) 4956(8) 6492(5) 55(2)

C(10B) 5888(9) 7932(7) 7994(5) 45(2) C(11B) 5344(9) 8050(7) 4353(5) 41(2) C(12B) 3854(9) 8170(7) 4817(5) 40(2) C(13B) 3166(10) 8954(7) 4427(5) 40(2) C(14B) 5475(9) 8769(7) 3702(5) 39(2) C(15B) 6623(10) 9016(7) 3014(5) 49(2) C(16B) 1611(10) 9396(8) 4566(5) 48(2) Bond lengths [A] and angles [deg] for 28.

F(1A)-C(2A) 1.358(8) C(8B)-C(9B) 1.479(10) C(11A)-C(14A)-C(15A) 134.2(8) F(2A)-C(2A) 1.344(7) C(11B)-C(14B) 1.365(10) O(4A)-C(16A)-C(13A) 127.3(8) F(3A)-C(3A) 1.403(8) C(11B)-C(12B) 1.433(10) C(8B)-O(1B)-C(7B) 106.4(6) F(4A)-C(3A) 1.334(9) C(12B)-C(13B) 1.345(10) C(14B)-O(3B)-C(13B) 107.1(6) O(1A)-C(7A) 1.384(8) C(13B)-C(16B) 1.454(10) C(4B)-C(1B)-C(11B) 135.7(7) O(1A)-C(8A) 1.389(8) C(14B)-C(15B) 1.442(10) C(4B)-C(1B)-C(2B) 95.6(7) O(2A)-C(10A) 1.214(8) C(7A)-O(1A)-C(8A) 105.7(5) C(11B)-C(1B)-C(2B) 128.5(7) O(3A)-C(14A) 1.352(8) C(14A)-O(3A)-C(13A) 105.5(6) F(2B)-C(2B)-F(1B) 106.7(7) O(3A)-C(13A) 1.397(8) C(4A)-C(1A)-C(11A) 138.6(7) F(2B)-C(2B)-C(1B) 116.4(6) O(4A)-C(16A) 1.222(8) C(4A)-C(1A)-C(2A) 93.9(6) F(1B)-C(2B)-C(1B) 117.5(7) C(1A)-C(4A) 1.333(9) C(11A)-C(1A)-C(2A) 127.3(6) F(2B)-C(2B)-C(3B) 115.8(7) C(1A)-C(11A) 1.446(10) F(2A)-C(2A)-F(1A) 107.4(5) F(1B)-C(2B)-C(3B) 114.3(6) C(1A)-C(2A) 1.528(10) F(2A)-C(2A)-C(1A) 118.0(7) C(1B)-C(2B)-C(3B) 85.4(6) C(2A)-C(3A) 1.531(10) F(1A)-C(2A)-C(1A) 117.1(6) F(3B)-C(3B)-F(4B) 106.2(5) C(3A)-C(4A) 1.493(10) F(2A)-C(2A)-C(3A) 116.0(6) F(3B)-C(3B)-C(4B) 117.4(7) C(4A)-C(5A) 1.462(9) F(1A)-C(2A)-C(3A) 112.4(7) F(4B)-C(3B)-C(4B) 115.9(6) C(5A)-C(8A) 1.372(10) C(1A)-C(2A)-C(3A) 84.8(6) F(3B)-C(3B)-C(2B) 114.3(6) C(5A)-C(6A) 1.428(9) F(4A)-C(3A)-F(3A) 103.6(6) F(4B)-C(3B)-C(2B) 114.9(7) C(6A)-C(7A) 1.349(10) F(4A)-C(3A)-C(4A) 118.7(6) C(4B)-C(3B)-C(2B) 87.8(6) C(7A)-C(10A) 1.492(10) F(3A)-C(3A)-C(4A) 116.0(7) C(1B)-C(4B)-C(5B) 138.9(7) C(8A)-C(9A) 1.473(10) F(4A)-C(3A)-C(2A) 118.1(7) C(1B)-C(4B)-C(3B) 91.1(6) C(11A)-C(14A) 1.362(10) F(3A)-C(3A)-C(2A) 113.0(6) C(5B)-C(4B)-C(3B) 130.0(7) C(11A)-C(12A) 1.437(10) C(4A)-C(3A)-C(2A) 87.7(6) C(8B)-C(5B)-C(4B) 128.0(7) C(12A)-C(13A) 1.333(9) C(1A)-C(4A)-C(5A) 136.0(7) C(8B)-C(5B)-C(6B) 104.7(7) C(13A)-C(16A) 1.433(10) C(1A)-C(4A)-C(3A) 93.6(6) C(4B)-C(5B)-C(6B) 127.2(7) C(14A)-C(15A) 1.493(10) C(5A)-C(4A)-C(3A) 129.9(7) C(7B)-C(6B)-C(5B) 108.4(7) F(1B)-C(2B) 1.352(9) C(8A)-C(5A)-C(6A) 107.4(7) C(6B)-C(7B)-O(1B) 109.2(7) F(2B)-C(2B) 1.344(8) C(8A)-C(5A)-C(4A) 124.6(7) C(6B)-C(7B)-C(10B) 133.2(8) F(3B)-C(3B) 1.361(9) C(6A)-C(5A)-C(4A) 127.9(7) O(1B)-C(7B)-C(10B) 117.5(7)

Appendix

F(4B)-C(3B) 1.362(7) C(7A)-C(6A)-C(5A) 105.9(7) O(1B)-C(8B)-C(5B) 111.3(6) O(1B)-C(8B) 1.353(8) C(6A)-C(7A)-O(1A) 111.6(6) O(1B)-C(8B)-C(9B) 115.8(7) O(1B)-C(7B) 1.408(8) C(6A)-C(7A)-C(10A) 130.3(7) C(5B)-C(8B)-C(9B) 132.9(7) O(2B)-C(10B) 1.229(8) O(1A)-C(7A)-C(10A) 118.0(6) O(2B)-C(10B)-C(7B) 127.1(8) O(3B)-C(14B) 1.380(8) C(5A)-C(8A)-O(1A) 109.3(7) C(14B)-C(11B)-C(12B) 107.9(7) O(3B)-C(13B) 1.387(9) C(5A)-C(8A)-C(9A) 134.8(7) C(14B)-C(11B)-C(1B) 125.3(7) O(4B)-C(16B) 1.222(9) O(1A)-C(8A)-C(9A) 115.7(7) C(12B)-C(11B)-C(1B) 126.7(8) C(1B)-C(4B) 1.357(10) O(2A)-C(10A)-C(7A) 122.8(7) C(13B)-C(12B)-C(11B) 106.1(7) C(1B)-C(11B) 1.484(10) C(14A)-C(11A)-C(12A) 104.7(7) C(12B)-C(13B)-O(3B) 110.4(6) C(1B)-C(2B) 1.504(10) C(14A)-C(11A)-C(1A) 128.2(7) C(12B)-C(13B)-C(16B) 132.8(8) C(2B)-C(3B) 1.535(11) C(12A)-C(11A)-C(1A) 126.6(7) O(3B)-C(13B)-C(16B) 116.7(7) C(3B)-C(4B) 1.526(10) C(13A)-C(12A)-C(11A) 107.7(7) C(11B)-C(14B)-O(3B) 108.5(6) C(4B)-C(5B) 1.402(10) C(12A)-C(13A)-O(3A) 110.1(7) C(11B)-C(14B)-C(15B) 135.0(7) C(5B)-C(8B) 1.374(10) C(12A)-C(13A)-C(16A) 131.6(7) O(3B)-C(14B)-C(15B) 116.5(7) C(5B)-C(6B) 1.442(10) O(3A)-C(13A)-C(16A) 118.2(7) O(4B)-C(16B)-C(13B) 125.0(8) C(6B)-C(7B) 1.331(10) O(3A)-C(14A)-C(11A) 112.0(7)

C(7B)-C(10B) 1.415(10) O(3A)-C(14A)-C(15A) 113.7(7)

Anisotropic displacement parameters (A^2 x 10^3) for 28. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]

U11 U22 U33 U23 U13 U12 F(1A) 42(3) 42(3) 72(3) 3(2) -4(2) 24(2) F(2A) 23(2) 69(4) 87(4) -3(3) -3(2) 31(2) F(3A) 45(3) 57(3) 72(3) -11(3) -17(2) 27(2) F(4A) 54(3) 76(4) 61(3) 9(3) 1(3) 36(3) O(1A) 26(3) 48(4) 54(4) -9(3) -3(2) 23(3) O(2A) 46(3) 63(4) 66(4) -8(3) -2(3) 37(3) O(3A) 27(3) 52(4) 63(4) 0(3) 5(3) 22(3) O(4A) 51(4) 68(5) 58(4) 9(3) 11(3) 29(3) C(1A) 21(4) 41(5) 50(6) 0(4) -4(3) 16(4) C(2A) 21(4) 39(6) 58(6) -1(4) -1(3) 20(4) C(3A) 35(5) 46(6) 59(6) 0(5) -8(4) 17(4) C(4A) 25(4) 51(6) 45(5) 7(4) 8(3) 26(4) C(5A) 23(4) 46(6) 54(6) -2(4) -3(4) 16(4) C(6A) 36(5) 49(6) 47(5) -7(4) -4(4) 22(4) C(7A) 40(5) 53(6) 50(6) -6(4) -4(4) 27(4) C(8A) 37(5) 52(6) 72(7) 5(5) 0(4) 25(4) C(9A) 49(5) 70(7) 50(6) 2(5) -4(4) 31(5)

C(10A) 47(5) 50(6) 53(6) -7(5) -14(4) 24(4)

Appendix

Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for 28.

x y z U(eq)

H(6A) -1595 7777 -258 50

H(9AA) 2818 9328 1978 80

H(9AB) 1407 8286 2437 80

H(9AC) 1250 9647 2479 80

H(10A) -4155 9092 11 58

H(12A) 640 8197 -1199 50

H(15A) 2156 4226 -1782 78

H(15B) 3085 4731 -927 78

H(15C) 4130 5133 -1744 78

Appendix

H(16A) 353 8520 -2837 51

H(6B) 5659 8224 6286 44

H(9BA) 7324 4316 6849 82

H(9BB) 9221 5223 6645 82

H(9BC) 7817 4640 5932 82

H(10B) 5334 8567 7941 54

H(12B) 3437 7776 5302 48

H(15D) 7873 9297 3200 73

H(15E) 6330 9644 2697 73

H(15F) 6447 8274 2677 73

H(16B) 942 9141 5037 58

Torsion angles [deg] for 28.

C(4A)-C(1A)-C(2A)-F(2A)a -116.5(7) C(4B)-C(1B)-C(2B)-F(2B) 118.8(8) C(11A)-C(1A)-C(2A)-F(2A) 59.9(10) C(11B)-C(1B)-C(2B)-F(2B) -57.0(12) C(4A)-C(1A)-C(2A)-F(1A) 112.9(7) C(4B)-C(1B)-C(2B)-F(1B) -112.9(8) C(11A)-C(1A)-C(2A)-F(1A) -70.8(10) C(11B)-C(1B)-C(2B)-F(1B) 71.3(11) C(4A)-C(1A)-C(2A)-C(3A) 0.3(6) C(4B)-C(1B)-C(2B)-C(3B) 2.2(7) C(11A)-C(1A)-C(2A)-C(3A) 176.7(8) C(11B)-C(1B)-C(2B)-C(3B) -173.6(8) F(2A)-C(2A)-C(3A)-F(4A) -120.0(7) F(2B)-C(2B)-C(3B)-F(3B) 0.0(9) F(1A)-C(2A)-C(3A)-F(4A) 4.1(9) F(1B)-C(2B)-C(3B)-F(3B) -124.6(7) C(1A)-C(2A)-C(3A)-F(4A) 121.3(7) C(1B)-C(2B)-C(3B)-F(3B) 117.2(6) F(2A)-C(2A)-C(3A)-F(3A) 1.0(10) F(2B)-C(2B)-C(3B)-F(4B) 123.2(7) F(1A)-C(2A)-C(3A)-F(3A) 125.1(6) F(1B)-C(2B)-C(3B)-F(4B) -1.4(10) C(1A)-C(2A)-C(3A)-F(3A) -117.6(7) C(1B)-C(2B)-C(3B)-F(4B) -119.6(7) F(2A)-C(2A)-C(3A)-C(4A) 118.4(7) F(2B)-C(2B)-C(3B)-C(4B) -119.2(7) F(1A)-C(2A)-C(3A)-C(4A) -117.5(6) F(1B)-C(2B)-C(3B)-C(4B) 116.2(7) C(1A)-C(2A)-C(3A)-C(4A) -0.3(6) C(1B)-C(2B)-C(3B)-C(4B) -1.9(6) C(11A)-C(1A)-C(4A)-C(5A) 12.2(17) C(11B)-C(1B)-C(4B)-C(5B) -9.3(17) C(2A)-C(1A)-C(4A)-C(5A) -172.1(9) C(2B)-C(1B)-C(4B)-C(5B) 175.3(10) C(11A)-C(1A)-C(4A)-C(3A) -176.0(10) C(11B)-C(1B)-C(4B)-C(3B) 173.1(9) C(2A)-C(1A)-C(4A)-C(3A) -0.3(7) C(2B)-C(1B)-C(4B)-C(3B) -2.2(7) F(4A)-C(3A)-C(4A)-C(1A) -120.7(7) F(3B)-C(3B)-C(4B)-C(1B) -114.2(7) F(3A)-C(3A)-C(4A)-C(1A) 114.9(7) F(4B)-C(3B)-C(4B)-C(1B) 118.9(7) C(2A)-C(3A)-C(4A)-C(1A) 0.3(7) C(2B)-C(3B)-C(4B)-C(1B) 2.2(6) F(4A)-C(3A)-C(4A)-C(5A) 51.8(12) F(3B)-C(3B)-C(4B)-C(5B) 67.9(10) F(3A)-C(3A)-C(4A)-C(5A) -72.5(11) F(4B)-C(3B)-C(4B)-C(5B) -59.0(12) C(2A)-C(3A)-C(4A)-C(5A) 172.9(8) C(2B)-C(3B)-C(4B)-C(5B) -175.7(8) C(1A)-C(4A)-C(5A)-C(8A) -161.1(9) C(1B)-C(4B)-C(5B)-C(8B) 173.8(9)

Appendix

C(3A)-C(4A)-C(5A)-C(6A) -149.4(9) C(3B)-C(4B)-C(5B)-C(6B) 166.2(7) C(8A)-C(5A)-C(6A)-C(7A) -1.9(10) C(8B)-C(5B)-C(6B)-C(7B) 1.0(8) C(4A)-C(5A)-C(6A)-C(7A) 177.3(8) C(4B)-C(5B)-C(6B)-C(7B) -175.4(7) C(5A)-C(6A)-C(7A)-O(1A) 1.3(10) C(5B)-C(6B)-C(7B)-O(1B) -0.8(8) C(5A)-C(6A)-C(7A)-C(10A) -175.7(9) C(5B)-C(6B)-C(7B)-C(10B) 176.5(8) C(8A)-O(1A)-C(7A)-C(6A) -0.2(9) C(8B)-O(1B)-C(7B)-C(6B) 0.3(8) C(8A)-O(1A)-C(7A)-C(10A) 177.1(8) C(8B)-O(1B)-C(7B)-C(10B) -177.5(6) C(6A)-C(5A)-C(8A)-O(1A) 1.8(10) C(7B)-O(1B)-C(8B)-C(5B) 0.4(8) C(4A)-C(5A)-C(8A)-O(1A) -177.4(7) C(7B)-O(1B)-C(8B)-C(9B) 178.1(7) C(6A)-C(5A)-C(8A)-C(9A) 177.8(9) C(4B)-C(5B)-C(8B)-O(1B) 175.5(7) C(4A)-C(5A)-C(8A)-C(9A) -1.3(16) C(6B)-C(5B)-C(8B)-O(1B) -0.9(8) C(7A)-O(1A)-C(8A)-C(5A) -1.0(9) C(4B)-C(5B)-C(8B)-C(9B) -1.6(15) C(7A)-O(1A)-C(8A)-C(9A) -177.9(7) C(6B)-C(5B)-C(8B)-C(9B) -178.0(8) C(6A)-C(7A)-C(10A)-O(2A) 175.2(9) C(6B)-C(7B)-C(10B)-O(2B) -171.8(8) O(1A)-C(7A)-C(10A)-O(2A) -1.6(13) O(1B)-C(7B)-C(10B)-O(2B) 5.3(12) C(4A)-C(1A)-C(11A)-C(14A) -177.5(9) C(4B)-C(1B)-C(11B)-C(14B) 159.9(9) C(2A)-C(1A)-C(11A)-C(14A) 8.0(13) C(2B)-C(1B)-C(11B)-C(14B) -26.1(13) C(4A)-C(1A)-C(11A)-C(12A) 11.4(15) C(4B)-C(1B)-C(11B)-C(12B) -23.9(15) C(2A)-C(1A)-C(11A)-C(12A) -163.2(7) C(2B)-C(1B)-C(11B)-C(12B) 150.1(8) C(14A)-C(11A)-C(12A)-C(13A) 1.0(8) C(14B)-C(11B)-C(12B)-C(13B) -0.2(9) C(1A)-C(11A)-C(12A)-C(13A) 173.9(7) C(1B)-C(11B)-C(12B)-C(13B) -176.9(7) C(11A)-C(12A)-C(13A)-O(3A) -0.2(8) C(11B)-C(12B)-C(13B)-O(3B) 0.5(8) C(11A)-C(12A)-C(13A)-C(16A) -176.1(7) C(11B)-C(12B)-C(13B)-C(16B) 176.3(8) C(14A)-O(3A)-C(13A)-C(12A) -0.7(8) C(14B)-O(3B)-C(13B)-C(12B) -0.6(8) C(14A)-O(3A)-C(13A)-C(16A) 175.9(6) C(14B)-O(3B)-C(13B)-C(16B) -177.2(6) C(13A)-O(3A)-C(14A)-C(11A) 1.4(8) C(12B)-C(11B)-C(14B)-O(3B) -0.2(9) C(13A)-O(3A)-C(14A)-C(15A) -179.2(6) C(1B)-C(11B)-C(14B)-O(3B) 176.6(6) C(12A)-C(11A)-C(14A)-O(3A) -1.5(8) C(12B)-C(11B)-C(14B)-C(15B) -177.8(8) C(1A)-C(11A)-C(14A)-O(3A) -174.2(7) C(1B)-C(11B)-C(14B)-C(15B) -1.0(15) C(12A)-C(11A)-C(14A)-C(15A) 179.2(8) C(13B)-O(3B)-C(14B)-C(11B) 0.4(8) C(1A)-C(11A)-C(14A)-C(15A) 6.5(14) C(13B)-O(3B)-C(14B)-C(15B) 178.6(6) C(12A)-C(13A)-C(16A)-O(4A) 168.6(8) C(12B)-C(13B)-C(16B)-O(4B) -175.7(8) O(3A)-C(13A)-C(16A)-O(4A) -7.1(11) O(3B)-C(13B)-C(16B)-O(4B) -0.1(12)

Appendix

O O

CF2

F₂ C F2C

O O O

O

Crystal data and structure refinement for 4a.

Empirical formula C21 H18 F6 O6

Formula weight 480.35

Temperature 293(2) K

Wavelength 0.71073 A

Crystal system Monoclinic

Space group C 2/c

Unit cell dimensions a = 21.390(4) A alpha= 90°.

b = 8.9727(10) A beta= 93.767(13)°.

c = 10.6721(18) A gamma = 90°.

Volume 2043.8(5) A^3

Z 4 Density (calculated) 1.561 Mg/m3

Absorption coefficient 0.148 mm-1

F(000) 984

Crystal size 0.4 x 0.3 x 0.2 mm3

Theta range for data collection 1.91 to 25.96°.

Index ranges -26<=h<=26, -11<=k<=0, 0<=l<=13 Reflections collected 2297

Independent reflections 1998 [R(int) = 0.0262]

Completeness to theta = 25.96° 99.9 % Absorption correction None

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1998 / 0 / 178

Goodness-of-fit on F2 1.034

Final R indices [I>2sigma(I)] R1 = 0.0513, wR2 = 0.1379 R indices (all data) R1 = 0.0838, wR2 = 0.1548 Largest diff. peak and hole 0.458 and -0.415 e.A-3

Appendix

Bond lengths [Å] and angles [°] for 4a.

C(1)-O(2) 1.409(3) C(5)#1-C(5)-C(6) 110.35(13) C(1)-O(3) 1.418(3) C(4)-C(5)-C(6) 119.2(2) C(1)-C(2) 1.498(3) F(2B)-C(6)-F(1A) 70.0(4) C(2)-C(3) 1.337(4) F(2B)-C(6)-F(1B) 106.3(4) C(2)-O(1) 1.379(3) F(2B)-C(6)-C(5) 119.8(3) C(3)-C(4) 1.446(3) F(1A)-C(6)-C(5) 116.3(3) C(4)-C(8) 1.359(3) F(1B)-C(6)-C(5) 107.7(3) C(4)-C(5) 1.458(3) F(2B)-C(6)-C(7) 117.7(3) C(5)-C(5)#1 1.355(4) F(1A)-C(6)-C(7) 123.7(3) C(5)-C(6) 1.496(3) F(1B)-C(6)-C(7) 95.9(3) C(6)-F(2B) 1.240(6) C(5)-C(6)-C(7) 106.4(2) C(6)-F(1A) 1.321(4) F(1A)-C(6)-F(2A) 100.2(4) C(6)-F(1B) 1.464(5) F(1B)-C(6)-F(2A) 136.0(3) C(6)-C(7) 1.501(4) C(5)-C(6)-F(2A) 105.2(3) C(6)-F(2A) 1.510(6) C(7)-C(6)-F(2A) 102.1(3) C(7)-F(3A) 1.266(5) F(3A)-C(7)-F(3A)#1 54.1(5) C(7)-C(6)#1 1.501(4) F(3A)-C(7)-C(6) 117.5(2) C(7)-F(3B) 1.504(4) F(3A)#1-C(7)-C(6) 127.5(2) C(8)-O(1) 1.368(3) C(6)-C(7)-C(6)#1 106.1(3) C(8)-C(9) 1.482(3) F(3A)-C(7)-F(3B) 50.6(2) C(10)-O(2) 1.444(4) F(3A)#1-C(7)-F(3B) 102.3(4) C(10)-C(11) 1.489(4) C(6)-C(7)-F(3B) 101.8(2) C(11)-O(3) 1.427(4) C(6)#1-C(7)-F(3B) 94.6(2)

O(2)-C(1)-O(3) 107.3(2) F(3B)#1-C(7)-F(3B) 152.6(5)

O(2)-C(1)-C(2) 112.5(2) C(4)-C(8)-O(1) 109.85(19)

O(3)-C(1)-C(2) 111.0(2) C(4)-C(8)-C(9) 134.6(2)

C(3)-C(2)-O(1) 110.7(2) O(1)-C(8)-C(9) 115.5(2)

C(3)-C(2)-C(1) 133.7(2) O(2)-C(10)-C(11) 102.1(2)

O(1)-C(2)-C(1) 115.7(2) O(3)-C(11)-C(10) 105.7(2)

C(2)-C(3)-C(4) 106.3(2) C(8)-O(1)-C(2) 106.79(18)

C(8)-C(4)-C(3) 106.4(2) C(1)-O(2)-C(10) 105.9(2)

C(8)-C(4)-C(5) 126.1(2) C(1)-O(3)-C(11) 107.7(2)

C(3)-C(4)-C(5) 127.3(2) F(3A)#1-F(3A)-C(7) 62.9(2) C(5)#1-C(5)-C(4) 130.42(13)

Appendix

O O

CF₂ F₂C

O O O

O

Crystal data and structure refinement for 27b.

Empirical formula C55 H67 F8 O12

Formula weight 1072.09

Temperature 100(2) K

Wavelength 0.71073 Е

Crystal system Triclinic

Space group P -1

Unit cell dimensions a = 10.9425(16) Е = 79.851(10)°.

b = 12.8801(16) Е = 89.064(11)°.

c = 20.430(3) Е  = 73.078(6)°.

Volume 2709.8(7) Е3

Z 2

Density (calculated) 1.314 Mg/m3

Absorption coefficient 0.109 mm-1

F(000) 1130

Crystal size 0.400 x 0.300 x 0.200 mm3

Theta range for data collection 1.80 to 26.90°.

Index ranges -13<=h<=13, -15<=k<=16, -25<=l<=25

Reflections collected 39119

Independent reflections 11518 [R(int) = 0.1199]

Completeness to theta = 26.90° 98.4 %

Absorption correction Integration

Max. and min. transmission 0.9607 and 0.7936

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 11518 / 0 / 688

Goodness-of-fit on F2 0.938

Appendix

Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Е2x 103) for 27b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

__________________________________________________________________

Appendix

Appendix

C(12)-C(13) 1.354(4) O(2)-C(5)-C(7) 109.3(2) C(40)-C(39)-C(38) 105.6(3) C(12)-C(15) 1.497(4) O(1)-C(5)-C(7) 106.8(2) C(42)-C(39)-C(38) 126.7(3) C(13)-C(16) 1.458(4) O(2)-C(5)-H(5) 109.4 O(9)-C(40)-C(39) 110.0(2) C(17)-C(18) 1.336(4) C(8)-C(7)-O(3) 110.5(2) C(43)-C(42)-C(39) 136.1(3) C(17)-H(17) 0.9500 C(8)-C(7)-C(5) 133.3(3) C(43)-C(42)-C(45) 92.3(3) C(18)-O(4) 1.369(3) O(3)-C(7)-C(5) 116.1(2) C(39)-C(42)-C(45) 131.3(3) C(18)-C(21) 1.496(4) C(7)-C(8)-C(9) 106.5(2) C(42)-C(43)-C(46) 135.0(3) C(19)-O(4) 1.377(3) C(7)-C(8)-H(8) 126.7 C(42)-C(43)-C(44) 93.8(2)

Appendix

C(21)-O(5) 1.418(3) C(9)-C(10)-C(11) 134.0(3) F(6)-C(44)-C(45) 115.6(3) C(21)-H(21) 1.0000 O(3)-C(10)-C(11) 116.0(3) C(43)-C(44)-C(45) 86.8(2) C(22)-O(5) 1.447(3) C(10)-C(11)-H(11A) 109.5 F(7)-C(45)-F(8) 105.2(2) C(22)-C(23) 1.515(4) C(10)-C(11)-H(11B) 109.5 F(7)-C(45)-C(42) 116.2(3) C(22)-H(22A) 0.9900 H(11A)-C(11)-H(11B) 109.5 F(8)-C(45)-C(42) 117.3(2) C(22)-H(22B) 0.9900 C(10)-C(11)-H(11C) 109.5 F(7)-C(45)-C(44) 115.8(2) C(23)-C(25) 1.530(4) H(11A)-C(11)-H(11C) 109.5 F(8)-C(45)-C(44) 115.1(3) C(23)-C(26) 1.532(4) H(11B)-C(11)-H(11C) 109.5 C(42)-C(45)-C(44) 87.2(2) C(23)-C(24) 1.534(4) C(13)-C(12)-C(9) 135.7(3) C(47)-C(46)-C(48) 105.5(3) C(24)-O(6) 1.448(3) C(13)-C(12)-C(15) 93.4(2) C(47)-C(46)-C(43) 126.9(3) C(24)-H(24A) 0.9900 C(9)-C(12)-C(15) 130.6(3) C(48)-C(46)-C(43) 127.5(3) C(24)-H(24B) 0.9900 C(12)-C(13)-C(16) 135.3(3) C(46)-C(47)-O(10) 109.9(3) C(25)-H(25A) 0.9800 C(12)-C(13)-C(14) 93.4(2) C(46)-C(47)-C(50) 135.4(3) C(25)-H(25B) 0.9800 C(16)-C(13)-C(14) 131.2(3) O(10)-C(47)-C(50) 114.5(3) C(25)-H(25C) 0.9800 F(2)-C(14)-F(1) 104.9(2) C(49)-C(48)-C(46) 107.1(3) C(26)-H(26A) 0.9800 F(2)-C(14)-C(13) 117.0(2) C(49)-C(48)-H(48) 126.5 C(26)-H(26B) 0.9800 F(1)-C(14)-C(13) 118.1(3) C(46)-C(48)-H(48) 126.5 C(26)-H(26C) 0.9800 F(2)-C(14)-C(15) 113.9(3) C(48)-C(49)-O(10) 110.6(3) C(31)-C(33) 1.522(4) F(1)-C(14)-C(15) 116.1(2) C(48)-C(49)-C(51) 134.5(3) C(31)-H(31A) 0.9800 C(13)-C(14)-C(15) 86.7(2) O(10)-C(49)-C(51) 114.9(2) C(31)-H(31B) 0.9800 F(4)-C(15)-F(3) 105.2(2) C(47)-C(50)-H(50A) 109.5 C(31)-H(31C) 0.9800 F(4)-C(15)-C(12) 117.6(2) C(47)-C(50)-H(50B) 109.5 C(32)-C(33) 1.530(4) F(3)-C(15)-C(12) 117.1(3) H(50A)-C(50)-H(50B) 109.5 C(32)-H(32A) 0.9800 F(4)-C(15)-C(14) 116.1(3) C(47)-C(50)-H(50C) 109.5 C(32)-H(32B) 0.9800 F(3)-C(15)-C(14) 114.5(2) H(50A)-C(50)-H(50C) 109.5 C(32)-H(32C) 0.9800 C(12)-C(15)-C(14) 86.3(2) H(50B)-C(50)-H(50C) 109.5 C(33)-C(34) 1.528(4) C(19)-C(16)-C(17) 106.8(3) O(11)-C(51)-O(12) 112.8(3) C(33)-C(36) 1.537(4) C(19)-C(16)-C(13) 127.2(3) O(11)-C(51)-C(49) 108.3(2) C(34)-O(7) 1.431(4) C(17)-C(16)-C(13) 126.1(3) O(12)-C(51)-C(49) 107.7(2) C(34)-H(34A) 0.9900 C(18)-C(17)-C(16) 106.3(3) O(11)-C(51)-H(51) 109.3 C(34)-H(34B) 0.9900 C(18)-C(17)-H(17) 126.8 O(12)-C(51)-H(51) 109.3 C(35)-O(7) 1.398(3) C(16)-C(17)-H(17) 126.8 C(49)-C(51)-H(51) 109.3 C(35)-O(8) 1.415(3) C(17)-C(18)-O(4) 110.8(3) O(11)-C(52)-C(53) 111.3(2) C(35)-C(37) 1.482(4) C(17)-C(18)-C(21) 133.9(3) O(11)-C(52)-H(52A) 109.4 C(35)-H(35) 1.0000 O(4)-C(18)-C(21) 115.3(2) C(53)-C(52)-H(52A) 109.4 C(36)-O(8) 1.439(4) C(16)-C(19)-O(4) 109.0(3) O(11)-C(52)-H(52B) 109.4 C(36)-H(36A) 0.9900 C(16)-C(19)-C(20) 135.5(3) C(53)-C(52)-H(52B) 109.4 C(36)-H(36B) 0.9900 O(4)-C(19)-C(20) 115.5(3) H(52A)-C(52)-H(52B) 108.0 C(37)-C(38) 1.334(4) C(19)-C(20)-H(20A) 109.5 C(54)-C(53)-C(52) 107.1(3)

Appendix

C(38)-H(38) 0.9500 C(19)-C(20)-H(20C) 109.5 C(54)-C(53)-C(56) 109.1(3) C(39)-C(40) 1.367(4) H(20A)-C(20)-H(20C) 109.5 C(52)-C(53)-C(56) 109.6(2) C(39)-C(42) 1.432(4) H(20B)-C(20)-H(20C) 109.5 C(55)-C(53)-C(56) 109.4(3) C(40)-O(9) 1.364(4) O(6)-C(21)-O(5) 112.3(2) O(12)-C(54)-C(53) 111.7(2) C(40)-C(41) 1.493(4) O(6)-C(21)-C(18) 108.0(2) O(12)-C(54)-H(54A) 109.3 C(41)-H(41A) 0.9800 O(5)-C(21)-C(18) 107.9(2) C(53)-C(54)-H(54A) 109.3 C(41)-H(41B) 0.9800 O(6)-C(21)-H(21) 109.5 O(12)-C(54)-H(54B) 109.3 C(41)-H(41C) 0.9800 O(5)-C(21)-H(21) 109.5 C(53)-C(54)-H(54B) 109.3 C(42)-C(43) 1.367(4) C(18)-C(21)-H(21) 109.5 H(54A)-C(54)-H(54B) 107.9 C(42)-C(45) 1.503(4) O(5)-C(22)-C(23) 111.3(2) C(53)-C(55)-H(55A) 109.5 C(43)-C(46) 1.449(4) O(5)-C(22)-H(22A) 109.4 C(53)-C(55)-H(55B) 109.5 C(43)-C(44) 1.490(4) C(23)-C(22)-H(22A) 109.4 H(55A)-C(55)-H(55B) 109.5 C(44)-F(5) 1.362(3) O(5)-C(22)-H(22B) 109.4 C(53)-C(55)-H(55C) 109.5 C(44)-F(6) 1.365(4) C(23)-C(22)-H(22B) 109.4 H(55A)-C(55)-H(55C) 109.5 C(44)-C(45) 1.524(5) H(22A)-C(22)-H(22B) 108.0 H(55B)-C(55)-H(55C) 109.5 C(45)-F(7) 1.369(3) C(22)-C(23)-C(25) 111.0(3) C(53)-C(56)-H(56A) 109.5 C(45)-F(8) 1.370(3) C(22)-C(23)-C(26) 109.0(2) C(53)-C(56)-H(56B) 109.5 C(46)-C(47) 1.365(4) C(25)-C(23)-C(26) 111.0(2) H(56A)-C(56)-H(56B) 109.5 C(46)-C(48) 1.447(4) C(22)-C(23)-C(24) 107.4(2) C(53)-C(56)-H(56C) 109.5 C(47)-O(10) 1.376(4) C(25)-C(23)-C(24) 109.5(2) H(56A)-C(56)-H(56C) 109.5 C(47)-C(50) 1.488(4) C(26)-C(23)-C(24) 108.8(2) H(56B)-C(56)-H(56C) 109.5 C(48)-C(49) 1.336(4) O(6)-C(24)-C(23) 111.2(2) C(102)-C(101)-H(10A) 109.5 C(48)-H(48) 0.9500 O(6)-C(24)-H(24A) 109.4 C(102)-C(101)-H(10B) 109.5 C(49)-O(10) 1.368(4) C(23)-C(24)-H(24A) 109.4 H(10A)-C(101)-H(10B) 109.5 C(49)-C(51) 1.498(4) O(6)-C(24)-H(24B) 109.4 C(102)-C(101)-H(10C) 109.5 C(50)-H(50A) 0.9800 C(23)-C(24)-H(24B) 109.4 H(10A)-C(101)-H(10C) 109.5 C(50)-H(50B) 0.9800 H(24A)-C(24)-H(24B) 108.0 H(10B)-C(101)-H(10C) 109.5 C(50)-H(50C) 0.9800 C(23)-C(25)-H(25A) 109.5 C(101)-C(102)-C(103) 113.7(3) C(51)-O(11) 1.385(4) C(23)-C(25)-H(25B) 109.5 C(101)-C(102)-H(10D) 108.8 C(51)-O(12) 1.406(3) H(25A)-C(25)-H(25B) 109.5 C(103)-C(102)-H(10D) 108.8 C(51)-H(51) 1.0000 C(23)-C(25)-H(25C) 109.5 C(101)-C(102)-H(10E) 108.8 C(52)-O(11) 1.442(4) H(25A)-C(25)-H(25C) 109.5 C(103)-C(102)-H(10E) 108.8 C(52)-C(53) 1.517(5) H(25B)-C(25)-H(25C) 109.5 H(10D)-C(102)-H(10E) 107.7 C(52)-H(52A) 0.9900 C(23)-C(26)-H(26A) 109.5 C(103)#1-C(103)-C(102) 114.1(4) C(52)-H(52B) 0.9900 C(23)-C(26)-H(26B) 109.5 C(103)#1-C(103)-H(10F) 108.7 C(53)-C(54) 1.504(4) H(26A)-C(26)-H(26B) 109.5 C(102)-C(103)-H(10F) 108.7 C(53)-C(55) 1.523(5) C(23)-C(26)-H(26C) 109.5 C(103)#1-C(103)-H(10G) 108.7 C(53)-C(56) 1.546(4) H(26A)-C(26)-H(26C) 109.5 C(102)-C(103)-H(10G) 108.7 C(54)-O(12) 1.443(3) H(26B)-C(26)-H(26C) 109.5 H(10F)-C(103)-H(10G) 107.6 C(54)-H(54A) 0.9900 C(33)-C(31)-H(31A) 109.5 C(5)-O(1)-C(4) 110.4(2) C(54)-H(54B) 0.9900 C(33)-C(31)-H(31B) 109.5 C(5)-O(2)-C(6) 109.9(2) C(55)-H(55A) 0.9800 H(31A)-C(31)-H(31B) 109.5 C(7)-O(3)-C(10) 107.0(2)

Appendix

C(55)-H(55B) 0.9800 C(33)-C(31)-H(31C) 109.5 C(18)-O(4)-C(19) 107.1(2) C(55)-H(55C) 0.9800 H(31A)-C(31)-H(31C) 109.5 C(21)-O(5)-C(22) 109.9(2) C(56)-H(56A) 0.9800 H(31B)-C(31)-H(31C) 109.5 C(21)-O(6)-C(24) 110.0(2) C(56)-H(56B) 0.9800 C(33)-C(32)-H(32A) 109.5 C(35)-O(7)-C(34) 111.2(2) C(56)-H(56C) 0.9800 C(33)-C(32)-H(32B) 109.5 C(35)-O(8)-C(36) 110.6(2) C(101)-C(102) 1.515(5) H(32A)-C(32)-H(32B) 109.5 C(40)-O(9)-C(37) 106.9(2) C(101)-H(10A) 0.9800 C(33)-C(32)-H(32C) 109.5 C(49)-O(10)-C(47) 106.9(2) C(101)-H(10B) 0.9800 H(32A)-C(32)-H(32C) 109.5 C(51)-O(11)-C(52) 109.6(2) C(101)-H(10C) 0.9800 H(32B)-C(32)-H(32C) 109.5 C(51)-O(12)-C(54) 109.8(2)

Anisotropic displacement parameters (Е2x 103)for 27b. The anisotropic displacement factor exponent takes the form: -22[ h2a*2U11 + ... + 2 h k a* b* U12 ]

Appendix

C(43) 35(2) 21(2) 18(1) -2(1) -5(1) -7(1)

C(44) 49(2) 26(2) 26(2) 0(1) -3(2) -11(2)

C(45) 49(2) 24(2) 22(2) 2(1) -4(1) -18(2)

C(46) 30(2) 24(2) 20(2) -7(1) -3(1) -8(1)

C(47) 31(2) 31(2) 34(2) -12(1) -6(1) -7(2)

C(48) 26(2) 24(2) 25(2) -6(1) -3(1) -7(1)

C(49) 28(2) 31(2) 25(2) -9(1) 0(1) -7(1)

C(50) 32(2) 34(2) 59(2) -8(2) -9(2) -1(2)

C(51) 29(2) 39(2) 20(2) -7(1) 4(1) -14(2)

C(52) 44(2) 49(2) 37(2) 14(2) -7(2) -30(2)

C(53) 38(2) 31(2) 25(2) 2(1) 3(1) -15(2)

C(54) 35(2) 31(2) 41(2) -7(2) -3(2) -17(2)

C(55) 72(3) 29(2) 49(2) 3(2) 20(2) -5(2)

C(56) 50(2) 42(2) 33(2) 3(2) -3(2) -26(2)

C(101) 53(2) 57(3) 44(2) -10(2) 1(2) -9(2)

C(102) 54(2) 44(2) 32(2) -3(2) 1(2) -16(2)

C(103) 54(2) 35(2) 26(2) -6(2) 4(2) -14(2)

O(1) 30(1) 32(1) 39(1) 12(1) 2(1) -6(1)

O(2) 47(1) 20(1) 37(1) -2(1) 16(1) -4(1)

O(3) 26(1) 26(1) 28(1) 0(1) 0(1) -8(1)

O(4) 26(1) 23(1) 27(1) -1(1) 0(1) -7(1)

O(5) 32(1) 23(1) 20(1) -2(1) 3(1) -10(1)

O(6) 31(1) 26(1) 32(1) -9(1) 6(1) -12(1)

O(7) 31(1) 23(1) 27(1) -5(1) -5(1) -8(1)

O(8) 34(1) 24(1) 29(1) -5(1) -7(1) -6(1)

O(9) 26(1) 33(1) 29(1) -6(1) 2(1) -13(1)

O(10) 26(1) 34(1) 38(1) -11(1) 0(1) -9(1)

O(11) 35(1) 42(1) 39(1) 14(1) -9(1) -23(1)

O(12) 33(1) 29(1) 30(1) -5(1) -7(1) -12(1)

F(1) 46(1) 33(1) 33(1) 13(1) -8(1) -12(1)

F(2) 39(1) 23(1) 48(1) -9(1) 1(1) -5(1)

F(3) 39(1) 38(1) 36(1) 2(1) 6(1) -18(1)

F(4) 40(1) 28(1) 39(1) -7(1) -4(1) -14(1)

F(5) 55(1) 27(1) 43(1) 8(1) -6(1) -4(1)

F(6) 57(1) 32(1) 40(1) -15(1) 9(1) -18(1)

F(7) 62(1) 31(1) 27(1) 5(1) 4(1) -22(1)

F(8) 49(1) 37(1) 32(1) -7(1) -3(1) -24(1)

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Appendix

S S

CF₂ F₂C

O O

Crystal data and structure refinement for 31.

Empirical formula C16 H10 F4 O2 S2

Formula weight 374.36

Temperature 100(2) K

Wavelength 0.71073 Е

Crystal system Monoclinic

Space group C 2/c

Unit cell dimensions a = 21.146(3) Е = 90°.

b = 8.0742(8) Е = 112.593(12)°.

c = 9.9346(17) Е  = 90°.

Volume 1566.0(4) Е3

Z 4 Density (calculated) 1.588 Mg/m3

Absorption coefficient 0.390 mm-1

F(000) 760 Crystal size 0.400 x 0.300 x 0.200 mm3

Theta range for data collection 2.09 to 26.71°.

Index ranges -26<=h<=26, -10<=k<=10, -12<=l<=12 Reflections collected 9953

Independent reflections 1648 [R(int) = 0.0813]

Completeness to theta = 26.90° 99.5 % Absorption correction Integration

Max. and min. transmission 0.9834 and 0.9073

Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 1648 / 0 / 110

Goodness-of-fit on F2 1.078

Final R indices [I>2sigma(I)] R1 = 0.0380, wR2 = 0.0902 R indices (all data) R1 = 0.0500, wR2 = 0.0939 Largest diff. peak and hole 0.312 and -0.269 e.Е-3

Appendix

Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Е2x 103) for 31. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

_____________________________________________________________________________

F(1)-C(8) 1.360(2) C(1)-C(2)-S(1) 121.35(17)

F(2)-C(8) 1.356(2) C(2)-C(3)-C(4) 112.55(18)

O(1)-C(1) 1.211(3) C(2)-C(3)-H(3) 123.7

S(1)-C(5) 1.7188(19) C(4)-C(3)-H(3) 123.7

S(1)-C(2) 1.729(2) C(5)-C(4)-C(3) 112.32(17)

C(1)-C(2) 1.460(3) C(5)-C(4)-C(7) 125.70(17)

C(1)-H(1) 0.9300 C(3)-C(4)-C(7) 121.80(18)

C(2)-C(3) 1.362(3) C(4)-C(5)-C(6) 128.18(18)

C(3)-C(4) 1.431(3) C(4)-C(5)-S(1) 111.41(14)

C(3)-H(3) 0.9300 C(6)-C(5)-S(1) 120.21(15)

C(4)-C(5) 1.381(3) C(5)-C(6)-H(6A) 109.5

C(4)-C(7) 1.456(3) C(5)-C(6)-H(6B) 109.5

C(5)-C(6) 1.497(3) H(6A)-C(6)-H(6B) 109.5

C(6)-H(6A) 0.9600 C(5)-C(6)-H(6C) 109.5

C(6)-H(6B) 0.9600 H(6A)-C(6)-H(6C) 109.5

C(6)-H(6C) 0.9600 H(6B)-C(6)-H(6C) 109.5

C(7)-C(7)#1 1.357(4) C(7)#1-C(7)-C(4) 139.67(10)

C(7)-C(8) 1.503(3) C(7)#1-C(7)-C(8) 93.41(11)

C(8)-C(8)#1 1.540(4) C(4)-C(7)-C(8) 126.89(17)

C(5)-S(1)-C(2) 91.90(10) F(2)-C(8)-F(1) 105.84(16)

O(1)-C(1)-C(2) 124.3(2) F(2)-C(8)-C(7) 117.43(18)

O(1)-C(1)-H(1) 117.9 F(1)-C(8)-C(7) 116.26(17)

C(2)-C(1)-H(1) 117.9 F(2)-C(8)-C(8)#1 116.1(2)

C(3)-C(2)-C(1) 126.8(2) F(1)-C(8)-C(8)#1 114.5(2)

Appendix

C(3)-C(2)-S(1) 111.80(15) C(7)-C(8)-C(8)#1 86.42(11) Anisotropic displacement parameters (Е2x 103)for 31. The anisotropic displacement factor exponent takes the form: -22[ h2a*2U11 + ... + 2 h k a* b* U12 ]

_____________________________________________________________________________

U11 U22 U33 U23 U13 U12

_____________________________________________________________________________

F(1) 51(1) 30(1) 39(1) 14(1) 14(1) 1(1) F(2) 36(1) 26(1) 59(1) -4(1) 20(1) 7(1) O(1) 31(1) 47(1) 35(1) -13(1) 4(1) -3(1) S(1) 23(1) 26(1) 28(1) -4(1) 7(1) -3(1) C(1) 26(1) 38(1) 28(1) -7(1) 6(1) 5(1) C(2) 23(1) 30(1) 23(1) -2(1) 7(1) 5(1) C(3) 25(1) 25(1) 24(1) 2(1) 9(1) 6(1) C(4) 20(1) 22(1) 22(1) 0(1) 9(1) 3(1) C(5) 22(1) 23(1) 24(1) -2(1) 9(1) 0(1) C(6) 32(1) 26(1) 25(1) 2(1) 8(1) -5(1) C(7) 26(1) 19(1) 22(1) 1(1) 10(1) 1(1) C(8) 31(1) 19(1) 34(1) 3(1) 13(1) 4(1)

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Appendix

O O

CF2

F₂ C F₂C

CHO OHC

Crystal data and structure refinement for 11.

Empirical formula C17 H10 F6 O4

Formula weight 392.25

Temperature 293(2) K

Wavelength 0.71073 A

Crystal system orthorhombic

Space group Fdd2

Unit cell dimensions

a = 27.865(3) A alpha = 90 deg.

b = 7.7268(7) A beta = 90 deg.

c = 15.3506(12) A gamma = 90 deg.

Volume 3305.1(5) A^3

Z 8 Calculated density 1.577 Mg/m^3

Absorption coefficient 0.155 mm^-1

F(000) 1584

Crystal size 0.20 x 0.05 x 0.05 mm

Theta range for data collection 2.92 to 29.99 deg.

Limiting indices -37<=h<=39, -10<=k<=10, -21<=l<=21 Reflections collected / unique 9125 / 2370 [R(int) = 0.0265]

Completeness to theta = 29.99 98.7 %

Max. and min. transmission 0.9923 and 0.9696

Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 2370 / 3 / 124

Goodness-of-fit on F^2 1.052

Final R indices [I>2sigma(I)] R1 = 0.0467, wR2 = 0.1213 R indices (all data) R1 = 0.0650, wR2 = 0.1299 Absolute structure parameter 1.8(9)

Largest diff. peak and hole 0.439 and -0.373 e.A^-3

Appendix

Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for 11. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

_ x y z U(eq)

F(1) 4711(1) 6007(1) 6189(1) 192(1)

F(2) 5198(1) 7803(2) 5239(1) 100(1)

F(3) 5771(1) 5953(2) 5304(1) 75(1)

O(1) 5929(1) 6501(1) 2299(1) 44(1)

O(2) 6520(1) 9322(2) 1796(1) 73(1)

C(1) 5000 5000 5711(1) 75(1)

C(2) 5305(1) 6127(1) 5106(1) 50(1)

C(3) 5183(1) 5568(2) 4200(1) 41(1)

C(4) 5474(1) 6272(2) 3489(1) 40(1)

C(5) 5689(1) 7950(2) 3483(1) 46(1)

C(6) 5961(1) 8022(2) 2753(1) 46(1)

C(7) 5633(1) 5435(2) 2760(1) 40(1)

C(8) 5564(1) 3679(2) 2402(1) 51(1)

C(9) 6272(1) 9382(2) 2443(1) 53(1)

Bond lengths [A] and angles [deg] for 11.

F(1)-C(1) 1.33997(11) C(6)-C(9) 1.443(2) C(3)#1-C(3)-C(4) 131.48(8) F(2)-C(2) 1.3448(13) C(7)-C(8) 1.476(2) C(3)#1-C(3)-C(2) 111.15(6) F(3)-C(2) 1.3390(10) C(7)-O(1)-C(6) 107.09(11) C(4)-C(3)-C(2) 117.35(11) O(1)-C(7) 1.3646(17) F(1)-C(1)-F(1)#1 113.49(2) C(7)-C(4)-C(5) 106.77(12) O(1)-C(6) 1.3691(19) F(1)-C(1)-C(2)#1 109.186(13) C(7)-C(4)-C(3) 127.85(13) O(2)-C(9) 1.212(2) F(1)#1-C(1)-C(2)#1 109.654(16) C(5)-C(4)-C(3) 125.08(13) C(1)-F(1)#1 1.33997(12) F(1)-C(1)-C(2) 109.654(16) C(6)-C(5)-C(4) 106.13(13) C(1)-C(2)#1 1.52998(13) F(1)#1-C(1)-C(2) 109.186(13) C(5)-C(6)-O(1) 110.45(13) C(1)-C(2) 1.52999(12) C(2)#1-C(1)-C(2) 105.36(2) C(5)-C(6)-C(9) 129.73(15) C(2)-C(3) 1.4968(15) F(3)-C(2)-F(2) 106.14(9) O(1)-C(6)-C(9) 119.77(14) C(3)-C(3)#1 1.344(3) F(3)-C(2)-C(3) 113.69(8) O(1)-C(7)-C(4) 109.54(12) C(3)-C(4) 1.464(2) F(2)-C(2)-C(3) 111.59(9) O(1)-C(7)-C(8) 116.21(13) C(4)-C(7) 1.367(2) F(3)-C(2)-C(1) 110.12(6) C(4)-C(7)-C(8) 134.22(14) C(4)-C(5) 1.428(2) F(2)-C(2)-C(1) 109.44(7) O(2)-C(9)-C(6) 125.82(16) C(5)-C(6) 1.354(2) C(3)-C(2)-C(1) 105.86(6)

Anisotropic displacement parameters (A^2 x 10^3) for 11. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]

U11 U22 U33 U23 U13 U12

Appendix

F(3) 44(1) 128(1) 51(1) -3(1) -10(1) -13(1)

O(1) 44(1) 50(1) 37(1) -4(1) 4(1) -5(1) O(2) 86(1) 70(1) 64(1) 0(1) 22(1) -19(1)

C(1) 55(1) 139(2) 32(1) 0 0 -23(2)

C(2) 45(1) 65(1) 38(1) -8(1) -3(1) 3(1) C(3) 36(1) 55(1) 33(1) -3(1) 0(1) 3(1) C(4) 37(1) 51(1) 33(1) -4(1) -1(1) -5(1) C(5) 48(1) 49(1) 41(1) -8(1) -3(1) -2(1) C(6) 46(1) 47(1) 46(1) -3(1) 2(1) -3(1) C(7) 35(1) 47(1) 38(1) -2(1) -2(1) -2(1) C(8) 49(1) 49(1) 55(1) -13(1) 6(1) 1(1) C(9) 55(1) 52(1) 52(1) 0(1) 4(1) -10(1) Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for 11.

x y z U(eq)

H(5) 5649 8819 3896 55

H(8A) 5504 2883 2870 77 H(8B) 5847 3332 2093 77 H(8C) 5295 3680 2011 77

H(9) 6284 10394 2770 64

Torsion angles [deg] for 11.

F(1)-C(1)-C(2)-F(3) 117.02(6) C(3)#1-C(3)-C(4)-C(5) 149.7(2) F(1)#1-C(1)-C(2)-F(3) -7.90(6) C(2)-C(3)-C(4)-C(5) -32.2(2) C(2)#1-C(1)-C(2)-F(3) -125.60(6) C(7)-C(4)-C(5)-C(6) 0.11(17) F(1)-C(1)-C(2)-F(2) 0.71(7) C(3)-C(4)-C(5)-C(6) 174.31(14) F(1)#1-C(1)-C(2)-F(2) -124.20(7) C(4)-C(5)-C(6)-O(1) 0.34(17) C(2)#1-C(1)-C(2)-F(2) 118.09(7) C(4)-C(5)-C(6)-C(9) -177.00(15) F(1)-C(1)-C(2)-C(3) -119.68(6) C(7)-O(1)-C(6)-C(5) -0.67(16) F(1)#1-C(1)-C(2)-C(3) 115.40(6) C(7)-O(1)-C(6)-C(9) 176.98(13) C(2)#1-C(1)-C(2)-C(3) -2.30(6) C(6)-O(1)-C(7)-C(4) 0.74(15) F(3)-C(2)-C(3)-C(3)#1 127.79(15) C(6)-O(1)-C(7)-C(8) -177.49(13) F(2)-C(2)-C(3)-C(3)#1 -112.20(16) C(5)-C(4)-C(7)-O(1) -0.53(16) C(1)-C(2)-C(3)-C(3)#1 6.78(17) C(3)-C(4)-C(7)-O(1) -174.52(13) F(3)-C(2)-C(3)-C(4) -50.63(14) C(5)-C(4)-C(7)-C(8) 177.25(16) F(2)-C(2)-C(3)-C(4) 69.38(14) C(3)-C(4)-C(7)-C(8) 3.3(3) C(1)-C(2)-C(3)-C(4) -171.64(10) C(5)-C(6)-C(9)-O(2) 176.96(18) C(3)#1-C(3)-C(4)-C(7) -37.3(3) O(1)-C(6)-C(9)-O(2) -0.2(3) C(2)-C(3)-C(4)-C(7) 140.72(13)

Appendix

N N N N

CF₂ F2

F₂C C

Crystal data and structure refinement for 22.

Empirical formula C17 H18 F6 N4

Formula weight 392.35

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P 21/c

Unit cell dimensions a = 11.5145(10) Å = 90°.

b = 15.4197(10) Å = 90.580(7)°.

c = 10.0805(9) Å  = 90°.

Volume 1789.7(3) Å3

Z 4

Density (calculated) 1.449 Mg/m3

Absorption coefficient 0.133 mm-1

F(000) 800

Crystal size 0.3 x 0.2 x 0.2 mm3

Theta range for data collection 1.77 to 26.86°.

Index ranges -14<=h<=14, -19<=k<=19, -12<=l<=12

Reflections collected 24163

Independent reflections 3814 [R(int) = 0.0436]

Completeness to theta = 26.86° 98.7 %

Absorption correction Integration

Max. and min. transmission 0.9892 and 0.8994

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 3814 / 0 / 314

Goodness-of-fit on F2 1.037

Final R indices [I>2sigma(I)] R1 = 0.0424, wR2 = 0.0929

Appendix

Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 22. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

__________________________________________________________________________

F(1A)-C(5) 1.391(4) F(3A)-C(6A)-C(5) 135.2(5) F(2B)-C(5)-C(6A) 85.6(2) F(2A)-C(5) 1.379(3) F(3A)-C(6A)-C(7) 120.2(5) F(2A)-C(5)-C(6A) 111.3(2) F(3A)-C(6A) 1.102(6) C(5)-C(6A)-C(7) 101.6(3) F(1A)-C(5)-C(6A) 108.2(3) F(5A)-C(7) 1.315(3) C(7)-F(6B)-C(6B) 49.0(2) C(4)-C(5)-C(6A) 108.0(3) F(5A)-F(6A) 1.491(5) F(3B)-C(6B)-C(7) 133.7(5) F(1B)-C(5)-C(6B) 112.3(3)

Appendix

F(6A)-C(7) 1.347(3) F(3B)-C(6B)-C(5) 117.6(5) F(2B)-C(5)-C(6B) 108.0(2) C(6A)-C(5) 1.513(6) C(7)-C(6B)-C(5) 106.1(4) F(2A)-C(5)-C(6B) 130.5(3) C(6A)-C(7) 1.594(6) F(3B)-C(6B)-F(6B) 108.2(4) F(1A)-C(5)-C(6B) 90.1(3) F(1B)-C(5) 1.318(4) C(7)-C(6B)-F(6B) 47.2(2) C(4)-C(5)-C(6B) 102.8(2) F(2B)-C(5) 1.362(3) C(5)-C(6B)-F(6B) 127.5(3) F(5A)-C(7)-F(6A) 68.1(2) F(3B)-C(6B) 1.230(6) C(3)-N(1)-N(2) 112.79(12) F(5A)-C(7)-F(6B) 104.7(2) F(5B)-C(7) 1.406(3) C(3)-N(1)-C(15) 128.02(13) F(6A)-C(7)-F(5B) 102.7(3) F(6B)-C(7) 1.405(3) N(2)-N(1)-C(15) 119.04(12) F(6B)-C(7)-F(5B) 137.7(2) F(6B)-C(6B) 1.903(7) C(11)-N(2)-N(1) 105.21(12) F(5A)-C(7)-C(6B) 125.7(3) C(6B)-C(7) 1.445(7) C(10)-N(3)-N(4) 112.85(13) F(6A)-C(7)-C(6B) 117.3(3) C(6B)-C(5) 1.567(6) C(10)-N(3)-C(17) 127.60(13) F(6B)-C(7)-C(6B) 83.7(3) N(1)-C(3) 1.3452(18) N(4)-N(3)-C(17) 119.41(13) F(5B)-C(7)-C(6B) 109.6(3) N(1)-N(2) 1.3610(18) C(1)-N(4)-N(3) 104.97(12) F(5A)-C(7)-C(8) 120.60(17) N(1)-C(15) 1.4565(19) N(4)-C(1)-C(9) 110.91(14) F(6A)-C(7)-C(8) 114.37(16) N(2)-C(11) 1.332(2) N(4)-C(1)-C(16) 119.33(14) F(6B)-C(7)-C(8) 108.16(14) N(3)-C(10) 1.343(2) C(9)-C(1)-C(16) 129.64(15) F(5B)-C(7)-C(8) 106.18(16) N(3)-N(4) 1.3676(18) C(3)-C(2)-C(11) 105.18(13) C(6B)-C(7)-C(8) 106.1(3) N(3)-C(17) 1.455(2) C(3)-C(2)-C(4) 124.74(13) F(5A)-C(7)-C(6A) 111.5(3) N(4)-C(1) 1.331(2) C(11)-C(2)-C(4) 130.07(14) F(6A)-C(7)-C(6A) 132.4(3) C(1)-C(9) 1.421(2) N(1)-C(3)-C(2) 106.29(13) F(6B)-C(7)-C(6A) 104.7(3) C(1)-C(16) 1.502(2) N(1)-C(3)-C(13) 122.31(13) F(5B)-C(7)-C(6A) 88.6(2) C(2)-C(3) 1.388(2) C(2)-C(3)-C(13) 131.34(13) C(8)-C(7)-C(6A) 106.0(2) C(2)-C(11) 1.422(2) C(8)-C(4)-C(2) 126.68(14) C(4)-C(8)-C(9) 127.39(13) C(2)-C(4) 1.465(2) C(8)-C(4)-C(5) 110.71(13) C(4)-C(8)-C(7) 110.47(14) C(3)-C(13) 1.491(2) C(2)-C(4)-C(5) 122.44(13) C(9)-C(8)-C(7) 121.96(13) C(4)-C(8) 1.353(2) F(1B)-C(5)-F(2B) 108.1(2) C(10)-C(9)-C(1) 104.96(14) C(4)-C(5) 1.499(2) F(1B)-C(5)-F(2A) 76.6(2) C(10)-C(9)-C(8) 124.55(13) C(7)-C(8) 1.499(2) F(2B)-C(5)-F(1A) 132.8(2) C(1)-C(9)-C(8) 130.49(14) C(8)-C(9) 1.458(2) F(2A)-C(5)-F(1A) 103.3(2) N(3)-C(10)-C(9) 106.32(13) C(9)-C(10) 1.395(2) F(1B)-C(5)-C(4) 117.1(2) N(3)-C(10)-C(12) 122.51(14) C(10)-C(12) 1.494(2) F(2B)-C(5)-C(4) 108.03(17) C(9)-C(10)-C(12) 131.15(15) C(11)-C(14) 1.497(2) F(2A)-C(5)-C(4) 116.06(16) N(2)-C(11)-C(2) 110.52(14) C(7)-F(5A)-F(6A) 56.98(17) F(1A)-C(5)-C(4) 109.7(2) N(2)-C(11)-C(14) 119.02(13) C(7)-F(6A)-F(5A) 54.93(15) F(1B)-C(5)-C(6A) 124.5(3) C(2)-C(11)-C(14) 130.43(14)

Anisotropic displacement parameters (Å2x 103)for 22. The anisotropic displacement factor exponent takes the form: -22[ h2a*2U11 + ... + 2 h k a* b* U12 ]

_______________________________________________________________________

U11 U22 U33 U23 U13 U12

Appendix

F(3A) 106(3) 26(2) 42(2) -17(1) 8(2) -7(2) F(4A) 41(1) 58(2) 42(1) 5(1) -7(1) -26(1) F(5A) 54(2) 36(1) 16(1) -5(1) 2(1) -1(1) F(6A) 53(2) 42(1) 28(1) -6(1) -16(1) -8(1) C(6A) 34(3) 21(2) 30(2) -6(2) 1(2) -1(2)

F(1B) 59(2) 26(1) 34(2) 2(1) 4(1) -13(2) F(2B) 40(1) 34(2) 59(2) -10(1) -1(1) 10(1) F(3B) 75(2) 31(2) 38(2) -11(1) -7(2) -21(2) F(4B) 51(1) 41(1) 41(1) -3(1) 17(1) 17(1) F(5B) 58(2) 38(2) 38(2) -14(1) 27(1) -8(1) F(6B) 31(1) 45(2) 45(2) -14(1) -12(1) -2(1) C(6B) 43(3) 27(3) 34(2) -12(2) 1(3) -3(3) N(1) 23(1) 23(1) 21(1) -2(1) -3(1) 1(1) N(2) 31(1) 22(1) 21(1) 0(1) 0(1) 1(1) N(3) 24(1) 25(1) 21(1) 2(1) -1(1) 0(1) N(4) 27(1) 30(1) 20(1) 4(1) -1(1) -3(1) C(1) 26(1) 29(1) 18(1) 1(1) -3(1) -4(1) C(2) 28(1) 17(1) 21(1) 0(1) -2(1) 2(1) C(3) 24(1) 22(1) 21(1) -1(1) -2(1) 5(1) C(4) 25(1) 24(1) 22(1) -3(1) 3(1) -3(1) C(5) 28(1) 24(1) 28(1) -2(1) 3(1) -1(1) C(7) 29(1) 33(1) 23(1) -7(1) 2(1) -1(1) C(8) 22(1) 26(1) 21(1) -3(1) 2(1) -5(1) C(9) 24(1) 26(1) 17(1) 0(1) -4(1) -4(1) C(10) 20(1) 26(1) 20(1) 2(1) -5(1) -4(1) C(11) 33(1) 19(1) 21(1) 1(1) -2(1) 1(1) C(12) 26(1) 30(1) 23(1) 1(1) 1(1) -4(1) C(13) 26(1) 36(1) 26(1) -2(1) 2(1) -4(1)

C(14) 48(1) 34(1) 25(1) 1(1) 4(1) -13(1) C(15) 26(1) 29(1) 27(1) -6(1) -6(1) 1(1)

C(16) 38(1) 36(1) 22(1) 0(1) 6(1) -5(1) C(17) 31(1) 27(1) 32(1) 3(1) 0(1) 4(1)

____________________________________________________________________

Appendix

O O

CF₂ F2

F₂C C

NC CN

CN NC

Crystal data and structure refinement for 18.

Empirical formula C23 H10 F6 N4 O2

Formula weight 488.35

Temperature 100(2) K

Wavelength 0.71073 Е

Crystal system Monoclinic

Space group C 2/c

Unit cell dimensions

a = 21.890(4) Е = 90°. b = 9.2771(15) Е =

99.344(12)°. c = 10.6726(14) Е  = 90°.

Volume 2138.6(6) Е3

Z 4

Density (calculated) 1.517 Mg/m3

Absorption coefficient 0.135 mm-1

F(000) 984

Crystal size 0.400 x 0.267 x 0.100 mm3

Theta range for data collection 1.89 to 26.82°.

Index ranges -27<=h<=27, -11<=k<=11, -13<=l<=12

Reflections collected 14031

Independent reflections 2275 [R(int) = 0.2274]

Completeness to theta = 26.82° 99.2 %

Absorption correction Integration

Max. and min. transmission 0.9871 and 0.9315

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 2275 / 0 / 188

Goodness-of-fit on F2 0.985

Final R indices [I>2sigma(I)] R1 = 0.0589, wR2 = 0.1048

Appendix

Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Е2x 103) for 18. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

___________________________________________________________________ F(2A)-C(8) 1.592(7) C(8)-F(1B)-F(2B) 50.4(3) F(2B)-C(8)-F(1A) 108.3(6) F(3A)-C(9) 1.403(4) C(8)-F(2B)-F(1B) 63.5(5) C(7)-C(8)-F(1A) 104.8(3) F(1B)-C(8) 1.334(4) C(9)-F(3B)-F(3B)#1 55.2(3) C(9)-C(8)-F(1A) 95.6(3) F(1B)-F(2B) 1.363(12) C(10)-O(1)-C(4) 106.92(18) F(1B)-C(8)-F(2A) 95.8(5) F(2B)-C(8) 1.150(6) N(2)-C(1)-C(2) 179.2(4) C(7)-C(8)-F(2A) 103.7(3) F(3B)-C(9) 1.327(5) C(3)-C(2)-C(12) 123.5(2) C(9)-C(8)-F(2A) 104.2(3) F(3B)-F(3B)#1 1.516(11) C(3)-C(2)-C(1) 120.6(3) F(1A)-C(8)-F(2A) 138.8(5) O(1)-C(10) 1.366(3) C(12)-C(2)-C(1) 115.9(2) F(3B)-C(9)-F(3B)#1 69.6(6) O(1)-C(4) 1.383(3) C(2)-C(3)-C(4) 129.2(2) F(3B)#1-C(9)-F(3A) 105.2(6) N(1)-C(12) 1.148(3) C(5)-C(4)-O(1) 109.7(2) F(3B)-C(9)-F(3A)#1 105.2(6) N(2)-C(1) 1.144(4) C(5)-C(4)-C(3) 130.7(2) F(3A)-C(9)-F(3A)#1 144.7(6) C(1)-C(2) 1.438(4) O(1)-C(4)-C(3) 119.5(2) F(3B)-C(9)-C(8)#1 113.1(2) C(2)-C(3) 1.346(4) C(4)-C(5)-C(6) 107.3(2) F(3B)#1-C(9)-C(8)#1 126.6(3) C(2)-C(12) 1.430(4) C(10)-C(6)-C(5) 106.2(2) F(3A)-C(9)-C(8)#1 105.9(2)

Appendix

C(3)-C(4) 1.430(4) C(10)-C(6)-C(7) 126.7(2) F(3A)#1-C(9)-C(8)#1 95.2(3) C(4)-C(5) 1.348(3) C(5)-C(6)-C(7) 127.0(2) F(3B)-C(9)-C(8) 126.6(3) C(5)-C(6) 1.427(3) C(7)#1-C(7)-C(6) 130.33(13) F(3B)#1-C(9)-C(8) 113.0(2) C(6)-C(10) 1.370(3) C(7)#1-C(7)-C(8) 110.52(16) F(3A)-C(9)-C(8) 95.2(3) C(6)-C(7) 1.461(3) C(6)-C(7)-C(8) 119.1(2) F(3A)#1-C(9)-C(8) 105.9(2) C(7)-C(7)#1 1.348(5) F(2B)-C(8)-F(1B) 66.1(6) C(8)#1-C(9)-C(8) 106.0(3) C(7)-C(8) 1.498(4) F(2B)-C(8)-C(7) 122.1(4) O(1)-C(10)-C(6) 109.9(2) C(8)-C(9) 1.504(4) F(1B)-C(8)-C(7) 116.9(3) O(1)-C(10)-C(11) 115.8(2) C(9)-F(3B)#1 1.327(5) F(2B)-C(8)-C(9) 115.8(3) C(6)-C(10)-C(11) 134.2(2) C(9)-F(3A)#1 1.403(4) F(1B)-C(8)-C(9) 126.0(3) N(1)-C(12)-C(2) 179.5(3) C(9)-C(8)#1 1.504(4)

Anisotropic displacement parameters (Е2x 103)for 18. The anisotropic displacement factor exponent takes the form: -22[ h2a*2U11 + ... + 2 h k a* b* U12 ]

________________________________________________________________________

U11 U22 U33 U23 U13 U12

________________________________________________________________________

F(1A) 52(2) 45(2) 59(4) 2(2) -15(2) -17(2) F(2A) 72(3) 36(2) 42(3) 10(2) 21(2) 0(2)

F(3A) 75(3) 49(3) 46(2) -13(2) 3(2) -18(2) F(1B) 46(2) 37(2) 84(5) 7(2) -4(2) -14(2) F(2B) 68(3) 37(2) 60(4) 10(2) 28(3) -4(2) F(3B) 89(3) 32(2) 67(3) -18(2) 27(3) -17(2) O(1) 30(1) 34(1) 37(1) 3(1) 14(1) 2(1) N(1) 47(1) 54(2) 48(2) -2(1) 16(1) 17(1) N(2) 48(2) 95(2) 72(2) -26(2) 32(2) -3(1) C(1) 37(2) 60(2) 48(2) -18(2) 13(1) -7(1) C(2) 29(1) 46(2) 34(2) -9(1) 11(1) -7(1) C(3) 33(1) 47(2) 31(1) -5(1) 11(1) -11(1) C(4) 30(1) 38(1) 31(1) 2(1) 12(1) -7(1)

C(5) 33(1) 41(1) 32(1) 6(1) 6(1) -11(1) C(6) 26(1) 28(1) 32(1) 0(1) 4(1) -6(1)

C(7) 35(1) 27(1) 31(1) 3(1) -2(1) -2(1) C(8) 41(2) 36(2) 93(3) 14(2) -1(2) -7(1) C(9) 84(3) 28(2) 37(2) 0 3(2) 0 C(10) 23(1) 32(1) 35(1) 1(1) 7(1) 2(1) C(11) 43(2) 40(2) 44(2) 10(1) 18(1) 11(1) C(12) 30(1) 44(2) 39(2) -12(1) 9(1) 9(1)

______________________________________________________________________________

Appendix

Selected UV-Vis data

Compound I0 313nm I0 438nm I0 576nm Copen, mol/l Cclosed, mol/l 27b 1,320×10^-8 1,488×10^-7 --- 3,89×10^-5 2,449×10^-5

31 1,027×10^-8 --- 1,975×10^-8 4,18×10^-5 5,971×10^-6 30 1,027×10^-8 --- 1,975×10^-8 4,40×10^-5 5,062×10^-6 29 1,019×10^-8 --- 1,890×10^-8 4,00×10^-5 3,964×10^-6 4b 1,320×10^-8 1,488×10^-7 --- 8,865×10^-5 7,683×10^-5

Absorption maxima and photoconversion quantum yields^[a]

Compound max(open) nm

max(open) M^-1cm^-1

max(closed) nm

max(closed) M^-1cm^-1

oc(1) co(2)

11 289 2.4010⁴ 533 0.9510⁴ 0.40 ^[b,c] 0.11 ^[d]

13 299 0.5910⁴ 455 0.7510⁴ 0.42 ^[b] 0.42 ^[d]

16 327 5.4610⁴ 576 1.5410⁴ 0.28 ^[b] 4.910^-3[f]

17 329 5.9810⁴ 575 1.7910⁴ 0.38 ^[b] 3.210^-3[f]

19 388 ^[h] 3.8010⁴ 667 0.5010⁴ 0.0015 ^[e] 7.210^-5[g]

21 341 4.7210⁴ 592 1.2910⁴ 0.69 ^[b] 1.610^-3[f]

20 360 2.8710⁴ 612 0.6210^{4 [i] [i]}

[a] All data for MeOH as the solvent, except for 11 and 31, in which CDCl3 was used. [b] Irradiation wavelength: 313 nm. [c] For the aldehyde 11, the switching reaction is photoreversible at 313 nm with

co(313) = 0.12. [d] 438 nm. [e] 366 nm. [f] 576 nm. [g] 633 nm (He/Ne-Laser). [h] This compound shows a double maximum at 388/409 nm. [i] more-step photoreaction, quantum yield not determined.

Appendix

Irradiation of 4b at 313 nm in methanol

300 400 500 600

Appendix

Irradiation of 27b at 313 nm in methanol

200 300 400 500 600

0,0

Irradiation of 31 at 313 nm in chloroform

300 400 500 600 700 800

0,0

Appendix Irradiation of 17 at 366 nm in methanol

1H NMR spectra of 17 (400 MHz, CD₃OD, 10^-3 M) recorded at different time intervals of irradiation with 366 nm

Im Dokument Synthesis and properties of photochromic difurylethenes for mechanically controlled break junctions (Seite 94-135)