Supporting Information for Advanced Materials, adma.200701772 Wiley-VCH 2007 69451 Weinheim, Germany
Supporting Information Oligo(p-phenylene vinylene)s as a New Class of Piezochromic Fluorophores Jill Kunzelman, Maki Kinami, Brent R. Crenshaw, John D. Protasiewicz, and Christoph Weder* Department of Macromolecular Science and Engineering and Department of Chemistry, Case Western Reserve University 2100 Adelbert Road, Cleveland, Ohio 44106-7202, USA Materials. All fluorophores were prepared as described before (C. Löwe, C. Weder, Adv. Mater. 2002, 14, 1625; M. Kinami, B. R. Crenshaw and C. Weder, Chem. Mater. 2006, 18, 946), with the only modification that C18-YB was recrystallized from 1-butanol. Optical Spectroscopy. Fluorescence spectra were acquired on a SPEX Fluorolog FL3-12 spectrometer ( ex = 375 nm for YB dyes and 435 for RG dyes, emission corrected for instrument throughput and detector response) using a Y-shaped optical fiber. For temperature-dependent experients, samples were placed on a Gel Instrumente AG hotstage with a TC2 temperature controller. Optical Microscopy. Polarization microscopy studies were conducted on an Olympus BX60 equipped with a Mettler FP82 hot stage and a Mettler FP80 controller with samples placed between crossed polarizers. Dynamic experiments were conducted at a heating rate of 10 C/min. Differential Scanning Calorimetry (DSC). DSC traces were recorded under a nitrogen atmosphere on a Perkin-Elmer DSC Pyris 1 at heating and cooling rates of 10 C/min. Wide Angle X-ray Diffraction. Wide angle X-ray diffraction (WAXD) measurements were conducted at RT on a Rigaku/MSC D/Max-Ultima Wide Angle Theta/Theta X-ray Diffraction System. Powder samples were loaded onto a rectangular glass sample holder and scans were obtained using CuK radiation with an incident wavelength of 0.15 nm under a voltage of 30 kv and a current of 30 ma. The scan rate was 0.5 /min. Single Crystal X-ray Diffraction. A lustrous, orange, block-like specimen of C1-RG, approximate dimensions 0.10 mm x 0.20 mm x 0.40 mm, was used for the X-ray crystallographic analysis. The X- ray intensity data were measured at 100(2) K on a Bruker SMART APEXII CCD area detector system equipped with a graphite monochromator and a Mo K fine-focus sealed tube ( = 0.71073Å) operated at 1.5 kw power (50 kv, 30 ma). The detector was placed at a distance of 6.00 cm from the crystal. A total of 2580 frames were collected with a scan width of 0.5º with an exposure time of 10.0 sec/frame. The total data collection time was 6 hours. The frames were integrated with the Bruker SAINT software package using a narrow-frame integration algorithm. The integration of the data using a triclinic unit cell yielded a total of 4531 reflections to a maximum angle of 28.54, of which 2501 were independent, completeness = 98.5%, R int = 1.76%, R sig = 1.95%) and 2203 were greater than 2 (I). The final cell constants of a = 4.5855(6) Å, b = 10.3518(13) Å, c = 12.9054(16) Å, = 68.45(10) = 88.001(2), = 77.3980(10) volume = 555.36 (12) Å 3, are based upon the refinement of the XYZ-centroids of 6465 reflections above 20 (I) with 3.40 < 2 < 55.0. Analysis of the data showed negligible decay during data collection. Data were corrected for absorption effects using the multi-scan technique (SADABS). The ratio of minimum to maximum apparent transmission 5
was 0.8940. The calculated minimum and maximum transmission coefficients (based on crystal size) are 0.9645 and 0.9909. The structure was solved and refined using the Bruker SHELXTL (Version 6.1) Software Package, using the space group P-1, with Z = 1 for the formula unit, C 28 H 24 N 2 O 4. The final anisotropic fullmatrix least-squares refinement on F 2 with 202 variables converged at R1 = 4.04%, for the observed data and wr2 = 9.79% for all data. The goodness-of-fit was 1.058. The largest peak on the final difference electron density synthesis was 0.321 e - /Å 3 and the largest hole was -0.200 e - /Å 3 with an RMS deviation of 0.004 e - /Å 3. All hydrogen atoms were located and positions refined. On the basis of the final model, the calculated density was 1.353 g/cm 3 and F(000), 238 e -. The structure shows evidence for weak bifurcated CH O hydrogen bonding (2.446 Å) between molecules involving the outermost methoxyaryl groups. The peripheral aromatic rings are offset by 23.7 from being coplanar with the central aromatic ring. The remaining bond distances and angles are relatively standard. 6
Figure S1. Packing down a-axis (top) and down b-axis (bottom) of C1-RG. 7
Table 1. Crystal data and structure refinement for C1-RG. Identification code Empirical formula test_0m C28 H24 N2 O4 Formula weight 452.49 Temperature Wavelength 100(2) K 0.71073 A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 4.5855(6) A alpha = 68.4500(10) deg. b = 10.3518(13) A beta = 88.001(2) deg. c = 12.9054(16) A gamma = 77.3980(10)deg. Volume 555.36(12) A^3 Z, Calculated density 1, 1.353 Mg/m^3 Absorption coefficient 0.091 mm^-1 F(000) 238 Crystal size Theta range for data collection Limiting indices 0.40 x 0.20 x 0.10 mm 1.70 to 27.50 deg. -5<=h<=5, -13<=k<=13, -16<=l<=16 Reflections collected / unique 6465 / 2501 [R(int) = 0.0176] Completeness to theta = 27.50 98.5 % Absorption correction Multi-scan Max. and min. transmission 0.9909 and 0.9645 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 2501 / 0 / 202 Goodness-of-fit on F^2 1.058 Final R indices [I>2sigma(I)] R1 = 0.0353, wr2 = 0.0937 R indices (all data) R1 = 0.0404, wr2 = 0.0979 Largest diff. peak and hole 0.321 and -0.200 e.a^-3 8
Table 2. Atomic coordinates (x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for C1-RG. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) C(1) 1763(3) 6793(1) 11706(1) 28(1) C(2) 3870(2) 8023(1) 10003(1) 17(1) C(3) 5597(3) 6774(1) 9942(1) 19(1) C(4) 7495(2) 6855(1) 9062(1) 18(1) C(5) 7749(2) 8157(1) 8254(1) 14(1) C(6) 5942(2) 9400(1) 8329(1) 15(1) C(7) 4008(2) 9336(1) 9180(1) 17(1) C(8) 9849(2) 8225(1) 7344(1) 14(1) C(9) 10761(2) 6923(1) 7136(1) 18(1) C(10) 10863(2) 9411(1) 6757(1) 14(1) C(11) 12935(2) 9681(1) 5861(1) 14(1) C(12) 14281(2) 8680(1) 5396(1) 15(1) C(13) 13709(2) 11024(1) 5439(1) 15(1) C(14) 13345(3) 13311(1) 5553(1) 24(1) N(1) 11401(3) 5868(1) 6990(1) 28(1) O(1) 1976(2) 8095(1) 10830(1) 22(1) O(2) 12380(2) 11995(1) 5903(1) 19(1) 9
Table 3. Bond lengths [Å] and angles [deg] for C1-RG. C(1)-O(1) 1.4259(14) C(1)-H(1) 0.974(17) C(1)-H(1A) 1.010(17) C(1)-H(1B) 0.980(17) C(2)-O(1) 1.3660(13) C(2)-C(3) 1.3892(16) C(2)-C(7) 1.3968(15) C(3)-C(4) 1.3951(15) C(3)-H(3) 0.976(15) C(4)-C(5) 1.3949(15) C(4)-H(4) 0.968(14) C(5)-C(6) 1.4048(15) C(5)-C(8) 1.4828(14) C(6)-C(7) 1.3786(15) C(6)-H(6) 0.971(14) C(7)-H(7) 0.964(14) C(8)-C(10) 1.3559(15) C(8)-C(9) 1.4410(15) C(9)-N(1) 1.1506(15) C(10)-C(11) 1.4563(14) C(10)-H(10) 0.952(14) C(11)-C(12) 1.4027(15) C(11)-C(13) 1.4139(14) C(12)-C(13)#1 1.3842(14) C(12)-H(12) 0.949(14) C(13)-O(2) 1.3749(12) C(13)-C(12)#1 1.3842(14) C(14)-O(2) 1.4331(13) C(14)-H(14A) 0.996(15) C(14)-H(14B) 1.012(15) C(14)-H(14C) 0.970(15) O(1)-C(1)-H(1) 111.3(10) O(1)-C(1)-H(1A) 111.2(9) H(1)-C(1)-H(1A) 108.9(13) O(1)-C(1)-H(1B) 103.9(9) H(1)-C(1)-H(1B) 110.3(13) H(1A)-C(1)-H(1B) 111.2(13) O(1)-C(2)-C(3) 125.00(10) O(1)-C(2)-C(7) 114.98(10) C(3)-C(2)-C(7) 120.01(10) C(2)-C(3)-C(4) 119.10(10) C(2)-C(3)-H(3) 121.9(8) C(4)-C(3)-H(3) 119.0(8) C(5)-C(4)-C(3) 121.83(10) C(5)-C(4)-H(4) 119.7(8) C(3)-C(4)-H(4) 118.4(8) C(4)-C(5)-C(6) 117.71(10) C(4)-C(5)-C(8) 121.10(9) C(6)-C(5)-C(8) 121.19(9) C(7)-C(6)-C(5) 121.13(10) C(7)-C(6)-H(6) 117.8(8) C(5)-C(6)-H(6) 121.0(8) C(6)-C(7)-C(2) 120.16(10) C(6)-C(7)-H(7) 121.0(8) C(2)-C(7)-H(7) 118.8(8) C(10)-C(8)-C(9) 122.26(10) C(10)-C(8)-C(5) 123.01(9) C(9)-C(8)-C(5) 114.72(9) N(1)-C(9)-C(8) 177.54(12) 10
C(8)-C(10)-C(11) 131.22(10) C(8)-C(10)-H(10) 115.9(8) C(11)-C(10)-H(10) 112.9(8) C(12)-C(11)-C(13) 117.19(9) C(12)-C(11)-C(10) 124.17(9) C(13)-C(11)-C(10) 118.63(9) C(13)#1-C(12)-C(11) 122.04(10) C(13)#1-C(12)-H(12) 117.9(8) C(11)-C(12)-H(12) 120.1(8) O(2)-C(13)-C(12)#1 122.60(9) O(2)-C(13)-C(11) 116.63(9) C(12)#1-C(13)-C(11) 120.77(10) O(2)-C(14)-H(14A) 109.6(8) O(2)-C(14)-H(14B) 111.6(8) H(14A)-C(14)-H(14B) 109.0(12) O(2)-C(14)-H(14C) 105.2(9) H(14A)-C(14)-H(14C) 109.3(12) H(14B)-C(14)-H(14C) 111.9(12) C(2)-O(1)-C(1) 117.82(9) C(13)-O(2)-C(14) 117.09(8) Symmetry transformations used to generate equivalent atoms: #1 -x+3,-y+2,-z+1 11
Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for C1-RG. The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U11 +... + 2 h k a* b* U12 ]. U11 U22 U33 U23 U13 U12 C(1) 33(1) 24(1) 22(1) -4(1) 13(1) -7(1) C(2) 16(1) 21(1) 16(1) -9(1) 5(1) -7(1) C(3) 22(1) 16(1) 18(1) -4(1) 5(1) -6(1) C(4) 19(1) 14(1) 20(1) -6(1) 4(1) -3(1) C(5) 14(1) 17(1) 14(1) -6(1) 1(1) -5(1) C(6) 17(1) 15(1) 14(1) -5(1) 1(1) -5(1) C(7) 17(1) 16(1) 18(1) -8(1) 2(1) -3(1) C(8) 14(1) 15(1) 14(1) -6(1) 1(1) -2(1) C(9) 20(1) 17(1) 17(1) -4(1) 7(1) -6(1) C(10) 14(1) 15(1) 15(1) -7(1) 1(1) -3(1) C(11) 13(1) 15(1) 13(1) -4(1) 1(1) -3(1) C(12) 16(1) 14(1) 15(1) -4(1) 2(1) -5(1) C(13) 15(1) 14(1) 15(1) -6(1) 1(1) -2(1) C(14) 34(1) 16(1) 27(1) -11(1) 12(1) -10(1) N(1) 37(1) 18(1) 29(1) -9(1) 17(1) -9(1) O(1) 27(1) 19(1) 20(1) -7(1) 13(1) -7(1) O(2) 25(1) 14(1) 21(1) -9(1) 10(1) -6(1) 12
Table 5. Hydrogen coordinates (x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for C1-RG. x y z U(eq) H(1) 3700(40) 6290(17) 12098(13) 35(4) H(3) 5540(30) 5841(16) 10502(12) 25(4) H(4) 8700(30) 5978(15) 9030(12) 24(3) H(6) 5950(30) 10330(15) 7764(11) 19(3) H(7) 2720(30) 10187(15) 9217(11) 21(3) H(10) 10180(30) 10208(15) 6973(11) 18(3) H(12) 13820(30) 7766(15) 5652(11) 21(3) H(1A) 990(40) 6148(18) 11409(14) 39(4) H(14A) 15540(30) 13114(15) 5712(12) 25(4) H(1B) 360(40) 7095(17) 12206(13) 37(4) H(14B) 12880(30) 13876(15) 4729(13) 26(4) H(14C) 12300(30) 13815(16) 6007(12) 27(4) 13
a b c 400 450 500 550 600 650 700 Figure S2. (a) Normalized fluorescence spectra of crystals (solid) and a CHCl 3 solution (dashed) of C18-YB. (b, c) Pictures taken under excitation (365 nm) of crystals (b) and a CHCl 3 solution (c) of C18-YB. 400 450 500 550 600 650 700 Figure S3. Normalized fluorescence spectra of a C18-YB/KBr mixture pressed for 1 min at 1500 psi (solid) and the same sample heated to 130 C (dashed). 14
400 450 500 550 600 650 700 Figure S4. Normalized fluorescence spectra of C18-YB as-prepared (solid), after grinding (dashed), and after grinding/heating to 130 C for 5 min (dotted). 400 450 500 550 600 650 700 Figure S5. Normalized fluorescence spectra of C18-YB slowly cooled from 145 C (solid) to 130 C (dashed) and to 35 C (dotted). 15
400 450 500 550 600 650 700 Figure S6. Normalized fluorescence spectra of C12-YB as-prepared (solid), pressed for 1 min at 1500 psi (dotted), pressed for 1 min at 1500 psi / heated to 130 C for 5 min (dashed), and the same sample subsequently heated to 155 C (dash-dotted). 5 10 15 20 25 30 2 (deg) Figure S7. Powder X-ray diffraction pattern of C18-YB pressed for 19.5 h at 1500 psi. 16
a b 450 500 550 600 650 700 750 800 400 450 500 550 600 650 700 c d 450 500 550 600 650 700 750 800 450 500 550 600 650 700 750 800 Figure S8. Normalized fluorescence spectra of (a) C1-RG, (b) C1-YB, (c) C18-RG as-prepared, and of (d) C18-RG recrystallized from 1-butanol (solid) and pressed for 5 min at 1500 psi (dashed). 17
a (a) 5 10 15 20 25 30 35 2 (deg) (b) b Figure S9. (a) X-ray diffraction patterns of C1-RG as-prepared (curve a) and of crystals grown by slow evaporation of a mixture of chloroform and hexanes (curve b). (b) X-ray diffraction pattern predicted by Mercury 1.4.2 of C1-RG based on single crystal data. 18