Supporting Information
Phosphorescent Organoplatinum(II) D2A2 Metallacycles: Synthesis, Self-Assembly and Photophysical Properties
YUZHEN ZHANG, JORDAN M. COX, ALAN E. FRIEDMAN, JASON B. BENEDICT and TIMOTHYR. COOK*
Table of ContentsFigure S1: 1H NMR spectrum of D1 / 2
Figure S2: 13C{1H} NMR spectrum of D1 / 3
Figure S3: 1H NMR spectrum of M1 (CDCl3) / 4
Figure S4: 1H NMR spectrum of M1 (CD2Cl2) / 4
Figure S5: 1H NMR spectrum of M2 (CD3CN) / 5
Figure S6: FT-ICR-MS of M1 / 6
Figure S7: Magnified FT-ICR-MS peaks of [M1-4OTf]4+ for M1 / 6
Figure S8: Magnified FT-ICR-MS peaks of [M1-3OTf]3+ for M1 / 7
Figure S9: FT-ICR-MS of M2 / 7
Figure S10: Magnified FT-ICR-MS peaks of [M2-4OTf]4+ for M2 / 8
Figure S11: Magnified FT-ICR-MS peaks of [2M2-3OTf]3+ for M2 / 8
Figure S12: UV-Vis spectra and emission for M1 and M2 in CH3CN / 9
Figure S13: UV-Vis spectra for D1 in different solvents / 10
Figure S14: Emission spectra for D1 in different solvents / 11
Figure S15: FTIR spectrum of M1 / 12
Figure S16: FTIR spectrum of M2 / 12
Tables S1-S6: Crystallographic Tables for D1 / 13-21
Figure S1: 1H NMR spectrum of D1 in CDCl3 at room temperature.
Figure S2: 13C{1H} NMR spectrum of D1 in CDCl3 at room temperature.
Figure S3: 1H NMR spectrum of M1 in CDCl3 at room temperature.
Figure S4: 1H NMR spectrum of M1 in CD2Cl2 at room temperature.
Figure S5: 1H NMR spectrum of M2 in CD3CN at room temperature.
Figure S6: FT-ICR-MS of M1.
Figure S7: Magnified FT-ICR-MS peaks of [M1-4OTf]4+ (667.80) for M1.
Figure S8: Magnified FT-ICR-MS peaks of [M1-3OTf]3+ (939.72) for of M1.
Figure S9: FT-ICR-MS of M2.
Figure S10: Magnified FT-ICR-MS peaks of [M2-4OTf]4+ for M2.
Figure S11: Magnified FT-ICR-MS peaks of [2M2-3OTf]3+ (1756.37) for M2.
Figure S12: Left: Absorption spectra of M1 (black solid, in CH3CN) and M2 (red solid, in CH3CN); Right: Emission spectra of M1 (black dashed, in CH3CN), M2 (red dashed, in CH3CN) in degassed solutions at room temperature.
Figure S13: Absorption spectra of D1 in toluene (black), methylene chloride (red), THF (blue), acetonitrile (cyan) and methanol (magenta) at room temperature.
Figure S14: Emission spectra of D1 in toluene (black), methylene chloride (red), THF (blue), acetonitrile (cyan) and methanol (magenta) at room temperature
Figure S15: FTIR spectrum of M1.
Figure S16: FTIR spectrum of M2.
Atom / x / y / z / U(eq)
Pt1 / 6556.9(2) / 3811.7(2) / 5183.0(2) / 7.95(2)
N1 / 6878.3(14) / 3360.6(13) / 133.8(10) / 20.8(3)
N2 / 981.8(15) / -1214.3(13) / 4580.1(12) / 24.5(3)
N3 / 8310.7(11) / 6105.0(11) / 5139.5(9) / 9.9(2)
N4 / 9281.0(12) / 5288.5(11) / 5961.3(9) / 10.9(2)
N5 / 6681.1(12) / 3612.5(11) / 7238.1(9) / 10.6(2)
N6 / 6505.4(12) / 5183.2(11) / 7105.0(9) / 10.4(2)
C1 / 6586.7(14) / 3481.9(12) / 3811.3(11) / 10.8(3)
C2 / 6629.5(14) / 3388.6(13) / 2984.8(11) / 12.7(3)
C3 / 6684.3(14) / 3352.4(13) / 2019.6(11) / 12.2(3)
C4 / 6221.0(16) / 4008.0(14) / 1510.8(12) / 16.2(3)
C5 / 6340.7(17) / 3983.5(15) / 593.8(12) / 20.1(3)
C6 / 7305.3(16) / 2725.3(15) / 615.0(12) / 18.9(3)
C7 / 7235.4(15) / 2688.7(14) / 1537.2(11) / 15.6(3)
C8 / 5029.3(14) / 2462.6(13) / 4919.7(10) / 11.1(3)
C9 / 4120.4(15) / 1638.9(13) / 4805.5(11) / 12.9(3)
C10 / 3063.8(14) / 676.3(13) / 4718.7(11) / 12.7(3)
C11 / 1869.2(15) / 562.9(14) / 4243.1(13) / 18.0(3)
C12 / 883.8(17) / -375.3(16) / 4197.6(14) / 23.5(4)
C13 / 2127.5(17) / -1107.2(15) / 5023.4(13) / 20.5(3)
C14 / 3169.7(15) / -202.9(14) / 5109.9(12) / 16.3(3)
C15 / 8140.2(14) / 5159.5(12) / 5448.8(10) / 9.6(3)
C16 / 9536.9(14) / 6811.6(13) / 5459.0(11) / 12.7(3)
C17 / 10147.1(14) / 6298.4(13) / 5972.9(11) / 13.4(3)
C18 / 7357.4(14) / 6359.9(13) / 4529.9(11) / 11.3(3)
C19 / 7698.9(15) / 6584.9(14) / 3626.2(11) / 13.3(3)
C20 / 6831.6(15) / 7015.8(14) / 3035.4(11) / 14.2(3)
C21 / 7192.8(15) / 7204.5(14) / 2123.9(11) / 14.5(3)
C22 / 6380.8(16) / 7652.7(14) / 1505.6(12) / 15.8(3)
C23 / 6693.3(17) / 7724.2(16) / 559.0(13) / 21.2(4)
C24 / 9586.7(15) / 4479.0(13) / 6429.6(11) / 12.9(3)
C25 / 9787.2(15) / 4821.6(14) / 7510.8(11) / 13.5(3)
C26 / 10220.0(15) / 4006.4(14) / 7978.2(11) / 14.9(3)
C27 / 10119.8(16) / 4139.7(15) / 9005.6(12) / 17.3(3)
C28 / 10561.9(18) / 3356.9(17) / 9514.3(13) / 23.0(4)
C29 / 9810(2) / 2111.9(17) / 9047.1(15) / 29.6(4)
C30 / 6560.8(13) / 4216.8(12) / 6589.8(10) / 9.4(3)
C31 / 6731.3(14) / 4201.2(13) / 8142.4(11) / 13.0(3)
C32 / 6610.2(14) / 5179.1(13) / 8056.7(11) / 13.0(3)
C33 / 6786.0(14) / 2498.0(13) / 7035.1(11) / 12.4(3)
C34 / 5862.3(16) / 1682.4(13) / 7384.5(12) / 15.6(3)
C35 / 5960.0(16) / 519.8(13) / 7220.8(12) / 16.3(3)
C36 / 5029.9(18) / -294.2(15) / 7587.0(13) / 20.9(3)
C37 / 5285.5(18) / -11.1(15) / 8682.0(13) / 22.5(4)
C38 / 6443(2) / -176.6(18) / 9173.5(14) / 31.0(5)
C39 / 6264.8(14) / 6069.9(13) / 6696.5(11) / 12.2(3)
C40 / 6977.4(15) / 7247.3(13) / 7371.0(12) / 14.3(3)
C41 / 8372.4(15) / 7575.7(13) / 7649.7(12) / 16.3(3)
C42 / 9032.7(16) / 8728.6(15) / 8378.3(13) / 20.3(3)
C43 / 10435.1(17) / 9086.3(16) / 8683.5(13) / 22.6(4)
C44 / 11041.1(18) / 9384.9(17) / 7901.9(15) / 27.2(4)
Table S2: Anisotropic Displacement Parameters (Å2×103) for D1. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].
Atom / U11 / U22 / U33 / U23 / U13 / U12
Pt1 / 8.51(3) / 7.73(3) / 7.22(2) / 2.54(2) / 2.61(2) / 1.82(2)
N1 / 24.3(8) / 23.8(8) / 11.3(6) / 5.8(6) / 5.4(6) / 3.7(6)
N2 / 18.9(7) / 19.9(8) / 30.0(9) / 12.2(7) / 5.3(6) / -1.8(6)
N3 / 8.7(6) / 9.9(6) / 9.5(5) / 3.1(4) / 2.1(4) / 1.4(5)
N4 / 10.0(6) / 11.8(6) / 9.9(6) / 3.3(5) / 2.0(5) / 2.8(5)
N5 / 12.0(6) / 10.8(6) / 9.1(5) / 3.4(5) / 3.5(5) / 3.3(5)
N6 / 11.9(6) / 9.9(6) / 8.7(5) / 2.9(4) / 2.9(5) / 2.5(5)
C1 / 10.4(6) / 8.6(6) / 12.2(7) / 3.0(5) / 2.5(5) / 1.9(5)
C2 / 12.6(7) / 12.7(7) / 12.4(7) / 3.9(5) / 3.7(5) / 3.3(6)
C3 / 11.6(7) / 12.1(7) / 8.4(6) / 1.8(5) / 1.5(5) / -0.5(5)
C4 / 18.4(8) / 16.9(8) / 12.8(7) / 3.5(6) / 4.7(6) / 5.9(6)
C5 / 24.1(9) / 20.2(8) / 14.5(8) / 7.6(6) / 2.6(6) / 5.9(7)
C6 / 22.0(8) / 22.0(8) / 12.2(7) / 2.6(6) / 7.3(6) / 6.9(7)
C7 / 18.4(8) / 16.5(8) / 10.5(7) / 3.5(6) / 3.7(6) / 4.4(6)
C8 / 13.0(7) / 10.7(7) / 8.7(6) / 2.2(5) / 3.3(5) / 3.2(5)
C9 / 13.3(7) / 12.4(7) / 12.7(7) / 2.5(5) / 4.1(5) / 4.4(6)
C10 / 13.1(7) / 10.0(7) / 11.8(7) / 0.5(5) / 5.1(5) / 0.4(6)
C11 / 15.5(8) / 15.1(8) / 20.9(8) / 6.7(6) / 4.1(6) / 1.5(6)
C12 / 14.8(8) / 22.1(9) / 29.4(10) / 12.1(8) / 2.3(7) / 0.2(7)
C13 / 21.2(8) / 15.7(8) / 23.5(9) / 9.9(7) / 6.1(7) / 2.4(7)
C14 / 15.2(7) / 15.4(8) / 18.1(8) / 6.1(6) / 4.6(6) / 4.4(6)
C15 / 10.8(6) / 9.8(6) / 7.7(6) / 2.4(5) / 2.9(5) / 2.7(5)
C16 / 9.8(7) / 12.2(7) / 13.3(7) / 3.3(6) / 3.3(5) / 0.1(5)
C17 / 10.3(7) / 14.8(7) / 11.8(7) / 2.6(6) / 2.7(5) / 0.9(6)
C18 / 11.4(7) / 12.0(7) / 11.4(6) / 4.5(5) / 3.0(5) / 4.6(5)
C19 / 12.8(7) / 15.6(7) / 13.1(7) / 6.4(6) / 4.0(6) / 5.4(6)
C20 / 15.7(7) / 15.8(7) / 13.7(7) / 6.6(6) / 5.2(6) / 7.0(6)
C21 / 15.8(7) / 17.0(8) / 13.8(7) / 7.5(6) / 6.3(6) / 6.7(6)
C22 / 17.7(8) / 18.3(8) / 16.0(7) / 9.1(6) / 6.2(6) / 8.9(6)
C23 / 23.5(9) / 27.0(9) / 17.6(8) / 12.4(7) / 7.5(7) / 10.1(7)
C24 / 14.8(7) / 15.8(7) / 10.5(6) / 5.1(6) / 2.4(5) / 8.4(6)
C25 / 13.0(7) / 15.9(7) / 11.3(7) / 4.1(6) / 2.3(5) / 5.5(6)
C26 / 14.1(7) / 20.6(8) / 13.0(7) / 6.6(6) / 4.0(6) / 9.0(6)
C27 / 19.0(8) / 23.1(8) / 12.8(7) / 6.9(6) / 6.0(6) / 9.6(7)
C28 / 24.9(9) / 34.8(10) / 16.5(8) / 13.8(8) / 7.4(7) / 15.2(8)
C29 / 40.3(12) / 28.6(10) / 28.2(10) / 16.9(9) / 14.2(9) / 15.4(9)
C30 / 8.6(6) / 9.4(6) / 10.4(6) / 4.1(5) / 3.5(5) / 1.8(5)
C31 / 14.2(7) / 14.4(7) / 10.0(6) / 4.7(5) / 4.6(5) / 3.0(6)
C32 / 15.1(7) / 13.4(7) / 8.9(6) / 1.5(5) / 4.7(5) / 3.1(6)
C33 / 14.2(7) / 12.4(7) / 13.5(7) / 5.8(6) / 6.2(6) / 5.8(6)
C34 / 18.8(8) / 12.9(7) / 18.7(8) / 6.6(6) / 9.6(6) / 6.3(6)
C35 / 24.2(8) / 12.4(7) / 15.0(7) / 5.1(6) / 8.7(6) / 7.5(6)
C36 / 26.5(9) / 13.4(8) / 21.5(8) / 6.2(6) / 8.4(7) / 3.5(7)
C37 / 29.8(10) / 15.9(8) / 25.3(9) / 10.1(7) / 15.1(8) / 5.6(7)
C38 / 50.7(14) / 31.4(11) / 22.7(9) / 14.9(8) / 14.2(9) / 23.6(10)
C39 / 13.4(7) / 12.1(7) / 12.1(7) / 3.3(5) / 3.3(5) / 6.0(6)
C40 / 16.8(7) / 11.7(7) / 15.3(7) / 3.7(6) / 5.0(6) / 6.1(6)
C41 / 17.9(8) / 11.1(7) / 18.3(8) / 3.4(6) / 4.4(6) / 3.9(6)
C42 / 21.3(9) / 16.6(8) / 18.1(8) / 0.5(6) / 2.5(7) / 4.4(7)
C43 / 20.0(9) / 18.1(8) / 21.5(9) / 2.5(7) / -1.2(7) / 1.5(7)
C44 / 21.9(9) / 21.0(9) / 30.8(10) / 3.7(8) / 4.7(8) / 0.4(7)
Atom / Atom / Length/Å / Atom / Atom / Length/Å
Pt1 / C1 / 1.9945(15) / C9 / C10 / 1.434(2)
Pt1 / C8 / 2.0005(15) / C10 / C11 / 1.404(2)
Pt1 / C15 / 2.0392(15) / C10 / C14 / 1.400(2)
Pt1 / C30 / 2.0379(15) / C11 / C12 / 1.382(2)
N1 / C5 / 1.341(2) / C13 / C14 / 1.381(2)
N1 / C6 / 1.335(2) / C16 / C17 / 1.349(2)
N2 / C12 / 1.343(2) / C18 / C19 / 1.521(2)
N2 / C13 / 1.342(2) / C19 / C20 / 1.525(2)
N3 / C15 / 1.3594(19) / C20 / C21 / 1.529(2)
N3 / C16 / 1.3871(19) / C21 / C22 / 1.519(2)
N3 / C18 / 1.4657(19) / C22 / C23 / 1.525(2)
N4 / C15 / 1.3594(19) / C24 / C25 / 1.519(2)
N4 / C17 / 1.387(2) / C25 / C26 / 1.528(2)
N4 / C24 / 1.4581(19) / C26 / C27 / 1.523(2)
N5 / C30 / 1.3604(19) / C27 / C28 / 1.529(2)
N5 / C31 / 1.3829(19) / C28 / C29 / 1.521(3)
N5 / C33 / 1.467(2) / C31 / C32 / 1.346(2)
N6 / C30 / 1.3619(19) / C33 / C34 / 1.517(2)
N6 / C32 / 1.3852(19) / C34 / C35 / 1.524(2)
N6 / C39 / 1.4723(19) / C35 / C36 / 1.535(2)
C1 / C2 / 1.214(2) / C36 / C37 / 1.531(3)
C2 / C3 / 1.429(2) / C37 / C38 / 1.522(3)
C3 / C4 / 1.401(2) / C39 / C40 / 1.523(2)
C3 / C7 / 1.404(2) / C40 / C41 / 1.526(2)
C4 / C5 / 1.382(2) / C41 / C42 / 1.526(2)
C6 / C7 / 1.387(2) / C42 / C43 / 1.531(3)
C8 / C9 / 1.217(2) / C43 / C44 / 1.523(3)
Table S4: Bond Angles for D1.
Atom / Atom / Atom / Angle/˚ / Atom / Atom / Atom / Angle/˚
C1 / Pt1 / C8 / 92.61(6) / C12 / C11 / C10 / 119.50(16)
C1 / Pt1 / C15 / 87.02(6) / N2 / C12 / C11 / 124.30(17)
C1 / Pt1 / C30 / 177.67(6) / N2 / C13 / C14 / 124.25(16)
C8 / Pt1 / C15 / 178.48(6) / C13 / C14 / C10 / 119.76(16)
C8 / Pt1 / C30 / 89.42(6) / N3 / C15 / Pt1 / 128.68(11)
C30 / Pt1 / C15 / 90.98(6) / N4 / C15 / Pt1 / 126.81(11)
C6 / N1 / C5 / 115.82(15) / N4 / C15 / N3 / 104.49(13)
C13 / N2 / C12 / 115.88(15) / C17 / C16 / N3 / 106.89(14)
C15 / N3 / C16 / 110.90(13) / C16 / C17 / N4 / 106.66(14)
C15 / N3 / C18 / 125.95(13) / N3 / C18 / C19 / 111.17(12)
C16 / N3 / C18 / 123.14(13) / C18 / C19 / C20 / 113.36(13)
C15 / N4 / C17 / 111.07(13) / C19 / C20 / C21 / 111.51(13)
C15 / N4 / C24 / 125.61(13) / C22 / C21 / C20 / 114.51(13)
C17 / N4 / C24 / 123.31(13) / C21 / C22 / C23 / 112.93(14)
C30 / N5 / C31 / 111.11(13) / N4 / C24 / C25 / 113.00(13)
C30 / N5 / C33 / 125.64(13) / C24 / C25 / C26 / 110.98(13)
C31 / N5 / C33 / 123.22(13) / C27 / C26 / C25 / 112.26(13)
C30 / N6 / C32 / 110.63(13) / C26 / C27 / C28 / 114.47(14)
C30 / N6 / C39 / 124.91(12) / C29 / C28 / C27 / 113.65(15)
C32 / N6 / C39 / 124.28(13) / N5 / C30 / Pt1 / 127.98(11)
C2 / C1 / Pt1 / 173.83(13) / N5 / C30 / N6 / 104.40(12)
C1 / C2 / C3 / 176.30(17) / N6 / C30 / Pt1 / 127.54(11)
C4 / C3 / C2 / 121.56(15) / C32 / C31 / N5 / 106.66(13)
C4 / C3 / C7 / 116.13(14) / C31 / C32 / N6 / 107.17(14)
C7 / C3 / C2 / 122.28(15) / N5 / C33 / C34 / 110.81(12)
C5 / C4 / C3 / 119.63(16) / C33 / C34 / C35 / 112.99(13)
N1 / C5 / C4 / 124.47(16) / C34 / C35 / C36 / 112.51(14)
N1 / C6 / C7 / 124.38(16) / C37 / C36 / C35 / 114.64(15)
C6 / C7 / C3 / 119.56(16) / C38 / C37 / C36 / 112.99(16)
C9 / C8 / Pt1 / 176.76(14) / N6 / C39 / C40 / 112.51(13)
C8 / C9 / C10 / 177.33(17) / C39 / C40 / C41 / 114.78(13)
C11 / C10 / C9 / 122.15(15) / C42 / C41 / C40 / 112.47(14)
C14 / C10 / C9 / 121.55(15) / C41 / C42 / C43 / 114.14(15)
C14 / C10 / C11 / 116.30(15) / C44 / C43 / C42 / 113.80(15)
Table S5: Torsion Angles for D1.
A / B / C / D / Angle/˚ / A / B / C / D / Angle/˚
N1 / C6 / C7 / C3 / 0.0(3) / C18 / N3 / C15 / N4 / 178.24(13)
N2 / C13 / C14 / C10 / -0.1(3) / C18 / N3 / C16 / C17 / -178.24(14)