イオン性高分子ポルフィリン金属錯体およびポリビピリジン

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1 2007 Excited State Properties of A Pyrene Derivative Containing Donor- and Acceptor- Functional Groups and Its Application as Photosensitizer

2 2

3 CH 3 N CH 3 H C C C 2 H 5 OOC COOC 2 H 5 3

4 Scheme 1 CH 3 N CH 3 Reaction Temp : Benzene reflux CH 3 N CH 3 + CH 2 (COOC 2 H 5 ) 2 NH piperidine : 4 drops AcOH : 2 drops : 30 ml HC O 460 mg (1.68 mmol) 222 mg (1.68 mmol) molecular sieve : 5g HC C C 2 H 5 OOC COOC 2 H 5 Yield ca 80% by NMR 4

5 Fig.1 5

6 CH 3 N c CH 3 a b H H 3 CH 2 COOC H 3 CH 2 COOC C C c CD 3 CN H 2 O b a 6

7 CH 3 N CH 3 H C C C 2 H 5 OOC COOC 2 H 5 7

8 2 17 CH 3 1 N 1 18 CH H 14 C19 15 C 20 C 2 H 5 OOC COOC 2 H 5 Fig.4 8

9 Solvent Heptane 1,4-Dioxane Toluene Diethyl Ether THF Dichloromethane Methanol Acetonitrile DMF N-Methyl formamide max 401nm 409nm 411nm 408nm 411nm 410nm 411nm 412nm 418nm 418nm Table.1 10 Max Absorbance Wavelength(nm) Fig.5 9

10 Solvent Heptane 1,4-Dioxane Toluene Diethyl Ether THF Dichloromethane Methanol Acetonitrile DMF N-Methyl formamide max 511nm 577nm 558nm 564nm 595nm 616nm 678nm 657nm 655nm 669nm Table.2 10 Max 10

11 Fluorescence Intensity Wavelength(nm) Fig

12 B3LYP/6-31+G(d) X f 2 = ( ε 1) /(2ε) ( n 1) / 2(2n 1) 2 f 12

13 1/cm Solvatochromic shift on the emission maxima Heptane 1,4-Dioxane Toluene Diethyl Ether THF Dichloromethane Methanol Acetonitrile DMF N-Methyl formamide f Fig ν max 3 = 1.2 / hcρ µ ( µ µ ) fconst 2 e e g 13

14 (Fig8)(Fig9) Absorbance 3 3 PMMA 2.5 AbsorptionSpectra in Polymer Films PMMA PS PSPE 2 PEPVA 1.5 PVA PA PAPVP PVP PEG PEG Absorbance Fluorescence Intensity Emission Spectra in Polymer Films PMMA PST PE PVA PA PVP PEG Wavelength(nm) 14

15 TRITONNX-100SDSCTAB) Absorbance Absorption Spectra in Micellar Solutions TRITONX-100 SDS CTAB Fig,9 sion Intensity EmissionSpectrain Micellar Solutions 15

16 Fig.10 Fig.11 AMP-CHO 16

17 ( I ph / e) IPCE( ) = 100 W /( hc / ) ph 17

18 Tris(2,2 -bipyridine)ru() AMP N3dye IPCE/% Wavelength/nm Fig.12 IPCE 5 AMP-Ester AMP-Ester IPCE 18

19 AMP-Ester X Table3,4 (Table5) (Table6)(Table6)AMP-Ester ORTEP Fig.13 Data Collection A reddish_yellow rod crystal of H 25 NO 4 C 26 having approximate dimensions of 0.25 x 0.25 x 0.25 mm was mounted on a glass fiber. All measurements were made on a Rigaku AFC7R diffractometer with graphite monochromated Mo-Kα radiation and a rotating anode generator. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using the setting angles of 25 carefully centered reflections in the range < 2θ < o corresponded to a primitive monoclinic cell with dimensions: a = 9.148(4) Å b = 7.199(2) Å β = 96.63(2) o c = (4) Å V = (12) Å 3 For Z = 4 and F.W. = , the calculated density is g/cm 3. The systematic absences of: h0l: l ± 2n 0k0: k ± 2n uniquely determine the space group to be: P2 1 /c (#14) 19

20 The data were collected at a temperature of o C using the ω scan technique to a maximum 2θ value of 55.0 o. Omega scans of several intense reflections, made prior to data collection, had an average width at half-height of 0.28 o with a take-off angle of 6.0 o. Scans of ( tan θ) o were made at a speed of 8.0 o /min (in ω). The weak reflections (I < 10.0σ(I)) were rescanned (maximum of 5 scans) and the counts were accumulated to ensure good counting statistics. Stationary background counts were recorded on each side of the reflection. The ratio of peak counting time to background counting time was 2:1. The diameter of the incident beam collimator was 0.5 mm and the crystal to detector distance was 235 mm. The computer-controlled slits were set to 3.0 mm (horizontal) and 3.0 mm (vertical). Data Reduction Of the 5341 reflections that were collected, 5029 were unique (R int = 0.120). The intensities of three representative reflections were measured after every 0 reflections. No decay correction was applied. The linear absorption coefficient, µ, for Mo-Kα radiation is cm -1. The data were corrected for Lorentz and polarization effects. Structure Solution and Refinement The structure was solved by direct methods 1 and expanded using Fourier techniques 2. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were refined using the riding model. The final cycle of full-matrix least-squares refinement 3 on F 2 was based on 2044 observed reflections and 305 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of: R1 = Σ Fo - Fc / Σ Fo =

21 wr2 = [ Σ ( w (Fo 2 - Fc 2 ) 2 )/ Σ w(fo 2 ) 2 ] 1/2 = The standard deviation of an observation of unit weight 4 was A Sheldrick weighting scheme was used. Plots of Σ w ( Fo - Fc ) 2 versus Fo, reflection order in data collection, sin θ/λ and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.23 and e - /Å 3, respectively. Neutral atom scattering factors were taken from Cromer and Waber 5. Anomalous dispersion effects were included in Fcalc 6 ; the values for f' and f" were those of Creagh and McAuley7. The values for the mass attenuation coefficients are those of Creagh and Hubbell 8. All calculations were performed using the CrystalStructure 9,10 crystallographic software package. Table 3. Atomic coordinates and B iso /B eq atom x y z B eq O(1) (3) (5) (9) 6.87(8) O(2) (3) (6) (8) 7.50(9) O(3) (3) (5) (8) 6.82(8) O(4) (3) (4) (7) 5.11(6) N(1) (4) (5) (10) 5.42(8) C(1) (4) (5) (11) 4.42(8) C(2) (4) (5) (11) 4.64(9) C(3) (4) (5) (10) 4.58(9) C(4) (4) (5) (10) 3.91(7) C(5) (4) (4) (10) 3.52(7) C(6) (4) (4) (10) 3.83(7) C(7) (4) (5) (11) 4.28(8) C(8) (4) (5) (11) 4.11(8) C(9) (3) (5) (10) 3.65(7) 21

22 C(10) (3) (4) (10) 3.45(7) C(11) (4) (5) (10) 3.86(8) C(12) (4) (5) (11) 4.51(9) C(13) (4) (5) (11) 4.47(9) C(14) (3) (4) (10) 3.74(7) C(15) (4) (5) (11) 4.41(9) C(16) (4) (5) (11) 4.51(9) C(17) (6) (7) (13) 6.86(12) C(18) (4) (7) (13) 5.92(11) C(19) (4) (5) (10) 4.02(7) C(20) (4) (5) (11) 4.31(8) C(21) (4) (6) (11) 4.90(9) C(22) (4) (6) (11) 4.44(8) C(23) (6) (15) (17) 12.7(2) C(24) (9) (11) (2) 12.9(2) C(25) (5) (8) (14) 7.21(14) C(26) (7) (10) (18) 11.2(2) Beq = 8/3 π 2 (U11(aa*) 2 + U22(bb*) 2 + U33(cc*) 2 + 2U12(aa*bb*)cos γ + 2U13(aa*cc*)cos β + 2U23(bb*cc*)cos α) 22

23 Table 4. Atomic coordinates and B iso involving hydrogens/b eq atom x y z B eq H(1) H(2) H(3) H(4) H(5) H(6) H(7) H(8) H(9) H(10) H(11) H(12) H(13) H(14) H(15) H(16) H(17) H(18) H(19) H(20) H(21) H(22) H(23) H(24) H(25) Beq = 8/3 π 2 (U11(aa*) 2 + U22(bb*) 2 + U33(cc*) 2 + 2U12(aa*bb*)cos γ + 2U13(aa*cc*)cos β + 2U23(bb*cc*)cos α) 23

24 Table 5. Bond lengths (Å) atom atom distance atom atom distance O(1) C(21) 1.187(5) O(2) C(21) 1.334(4) O(2) C(23) 1.445(6) O(3) C(22) 1.201(5) O(4) C(22) 1.321(5) O(4) C(25) 1.456(6) N(1) C(1) 1.422(5) N(1) C(17) 1.479(5) N(1) C(18) 1.462(6) C(1) C(2) 1.392(6) C(1) C(6) 1.420(4) C(2) C(3) 1.377(5) C(3) C(4) 1.399(4) C(4) C(5) 1.421(5) C(4) C(7) 1.414(5) C(5) C(6) 1.416(4) C(5) C(10) 1.438(4) C(6) C(13) 1.431(5) C(7) C(8) 1.352(5) C(8) C(9) 1.425(5) C(9) C(10) 1.421(4) C(9) C(14) 1.423(4) C(10) C(11) 1.422(5) C(11) C(12) 1.424(5) C(11) C(16) 1.396(4) C(12) C(13) 1.357(5) C(14) C(15) 1.394(5) C(14) C(19) 1.450(4) C(15) C(16) 1.367(5) C(19) C(20) 1.350(4) C(20) C(21) 1.497(5) C(20) C(22) 1.493(5) 24

25 C(23) C(24) 1.351(9) C(25) C(26) 1.433(9) Table 6. Bond angles ( o ) atom atom atom angle atom atom atom angle C(21) O(2) C(23) 116.5(4) C(22) O(4) C(25) 116.9(3) C(1) N(1) C(17) 115.3(3) C(1) N(1) C(18) 115.5(3) C(17) N(1) C(18) 111.5(3) N(1) C(1) C(2) 122.6(3) N(1) C(1) C(6) 118.3(3) C(2) C(1) C(6) 119.1(3) C(1) C(2) C(3) 121.6(3) C(2) C(3) C(4) 121.3(3) C(3) C(4) C(5) 118.0(3) C(3) C(4) C(7) 122.8(3) C(5) C(4) C(7) 119.2(3) C(4) C(5) C(6) 120.9(3) C(4) C(5) C(10) 118.7(3) C(6) C(5) C(10) 120.5(3) C(1) C(6) C(5) 119.0(3) C(1) C(6) C(13) 122.7(3) C(5) C(6) C(13) 118.3(3) C(4) C(7) C(8) 122.0(3) C(7) C(8) C(9) 121.5(3) C(8) C(9) C(10) 118.0(3) C(8) C(9) C(14) 123.1(3) C(10) C(9) C(14) 118.9(3) C(5) C(10) C(9) 120.7(3) C(5) C(10) C(11) 119.0(2) C(9) C(10) C(11) 120.3(3) C(10) C(11) C(12) 119.3(3) C(10) C(11) C(16) 118.9(3) C(12) C(11) C(16) 25

26 121.8(3) C(11) C(12) C(13) 121.2(3) C(6) C(13) C(12) 121.6(3) C(9) C(14) C(15) 118.8(3) C(9) C(14) C(19) 119.4(3) C(15) C(14) C(19) 121.8(3) C(14) C(15) C(16) 122.4(3) C(11) C(16) C(15) 120.6(3) C(14) C(19) C(20) 128.4(3) C(19) C(20) C(21) 117.8(3) C(19) C(20) C(22) 125.3(3) C(21) C(20) C(22) 116.9(3) O(1) C(21) O(2) 124.2(3) O(1) C(21) C(20) 124.8(3) O(2) C(21) C(20) 110.9(3) O(3) C(22) O(4) 124.6(3) O(3) C(22) C(20) 123.9(4) O(4) C(22) C(20) 111.5(3) O(2) C(23) C(24) 112.4(5) O(4) C(25) C(26) 108.9(4) Table 7. Torsion Angles( o ) atom1 atom2 atom3 atom4 angle atom1 atom2 atom3 atom4 angle C(21) O(2) C(23) C(24) (6) C(23) O(2) C(21) O(1) -0.4(7) C(23) O(2) C(21) C(20) (5) C(22) O(4) C(25) C(26) (4) C(25) O(4) C(22) O(3) -3.6(5) C(25) O(4) C(22) C(20) 174.5(3) C(17) N(1) C(1) C(2) 21.1(5) C(17) N(1) C(1) C(6) (3) C(18) N(1) C(1) C(2) (4) C(18) N(1) C(1) C(6) 68.7(4) 26

27 N(1) C(1) C(2) C(3) 177.9(3) N(1) C(1) C(6) C(5) (3) N(1) C(1) C(6) C(13) 5.6(5) C(2) C(1) C(6) C(5) 3.5(5) C(2) C(1) C(6) C(13) (3) C(6) C(1) C(2) C(3) -2.0(5) C(1) C(2) C(3) C(4) -0.6(6) C(2) C(3) C(4) C(5) 1.5(5) C(2) C(3) C(4) C(7) (3) C(3) C(4) C(5) C(6) 0.1(3) C(3) C(4) C(5) C(10) 179.5(3) C(3) C(4) C(7) C(8) 178.5(3) C(5) C(4) C(7) C(8) -1.0(5) C(7) C(4) C(5) C(6) 179.6(3) C(7) C(4) C(5) C(10) -1.0(5) C(4) C(5) C(6) C(1) -2.6(5) C(4) C(5) C(6) C(13) 175.5(3) C(4) C(5) C(10) C(9) 1.9(4) C(4) C(5) C(10) C(11) (3) C(6) C(5) C(10) C(9) (3) C(6) C(5) C(10) C(11) 1.2(4) C(10) C(5) C(6) C(1) 178.0(3) C(10) C(5) C(6) C(13) -3.9(5) C(1) C(6) C(13) C(12) (3) C(5) C(6) C(13) C(12) 2.9(5) C(4) C(7) C(8) C(9) 2.0(6) C(7) C(8) C(9) C(10) -1.1(5) C(7) C(8) C(9) C(14) (3) C(8) C(9) C(10) C(5) -0.9(5) C(8) C(9) C(10) C(11) 179.2(3) C(8) C(9) C(14) C(15) (3) C(8) C(9) C(14) C(19) -0.8(5) C(10) C(9) C(14) C(15) 2.0(5) C(10) C(9) C(14) C(19) (3) C(14) C(9) C(10) C(5) 177.2(3) C(14) C(9) C(10) C(11) -2.7(5) 27

28 C(5) C(10) C(11) C(12) 2.5(5) C(5) C(10) C(11) C(16) (3) C(9) C(10) C(11) C(12) (3) C(9) C(10) C(11) C(16) 0.5(5) C(10) C(11) C(12) C(13) -3.5(5) C(10) C(11) C(16) C(15) 2.5(5) C(12) C(11) C(16) C(15) (3) C(16) C(11) C(12) C(13) 178.5(3) C(11) C(12) C(13) C(6) 0.8(6) C(9) C(14) C(15) C(16) 1.0(5) C(9) C(14) C(19) C(20) 153.3(4) C(15) C(14) C(19) C(20) -27.5(6) C(19) C(14) C(15) C(16) (3) C(14) C(15) C(16) C(11) -3.3(6) C(14) C(19) C(20) C(21) 179.2(3) C(14) C(19) C(20) C(22) -2.0(6) C(19) C(20) C(21) O(1) -5.5(6) C(19) C(20) C(21) O(2) 172.2(3) C(19) C(20) C(22) O(3) 109.9(4) C(19) C(20) C(22) O(4) -68.2(5) C(21) C(20) C(22) O(3) -71.3(5) C(21) C(20) C(22) O(4) 110.6(3) C(22) C(20) C(21) O(1) 175.6(4) C(22) C(20) C(21) O(2) -6.7(5) The sign is positive if when looking from atom 2 to atom 3 a clock-wise motion of atom 1 would superimpose it on atom 4. 28

29 Fig.13 ORTEP 29

30 1. Alan R Katritzky, Dong-Wei Zhu, and Kirk S. Schanze:Intramolecular Charge Transfer Properties of Dicyanovinyl-Substltuted Aromatics,J.Phys.Chem. 1991, 95, Paul Liska, Nick Vlachopoulos, Mohammad K. Nazeeruddin, Pascal Comte, and Michael Gratzel : cis-diaquabis(2,2 -bpyridyl-4,4 -dicarboxylate)-ruthenium( ) Sensitizes Wide band Gap Oxide Semiconductors Very Efficiently over a Broad Spectral Range in the Visible, J. Am. Chem. Soc. 1988, 110, M. K. Nazeeruddin, A. Kay, I.Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, and M. Gratzel : Conversion of Light to Electricity by cis-x2bis(2,2 -bipyridyl-4,4 -dicarboxylate)ruthenium( ) Charge-Transfer Sensitizers (X=Cl -, Br -, I -, CN -, and SCN - ) on Nanocrystalline TiO2 Electrodes, J. Am. Chem. Soc. 1993, 115, Yuji Kawanishi, Noboru Kitamura, and Shingo Tazuke : Dependence of Spectroscopic, Electrochemical, and Excitd-State Properties of Tris Chelate Ruthenium() Complexes on Ligand Structure, Inorg. Chem. 1989, 28,

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