Synthesis, characterization and luminescence studies of

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1 Supporting Information for Synthesis, characterization and luminescence studies of gold(i) HC amide complexes Adrián Gómez-Suárez, David J. elson, David G. Thompson, David B. Cordes, Duncan Graham, Alexandra M. Z. Slawin and Steven P. olan* Address: EaStCHEM School of Chemistry, University of St Andrews, orth Haugh, St Andrews, Fife, KY6 9ST, UK and WestCHEM Department of Pure and Applied Chemistry and Centre for Molecular anometrology, University of Strathclyde, 9 Cathedral Street, Glasgow, G XL, UK Steven P. olan snolan@st-andrews.ac.uk * Corresponding author Experimental part S

2 Table of Contents General considerations:... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(phenylamino)gold Complex ():... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(pyridin--ylamino)gold complex ():... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(pyridin--ylamino)gold Complex ():... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(pyridin--ylamino)gold complex ():... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-methylpyridin-- yl)amino)gold Complex (6):... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-chloropyridin-- yl)amino)gold complex (7):... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((- (trifluoromethyl)pyridin--yl)amino)gold complex (8):... S Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-nitropyridin-- yl)amino)gold complex (9):... S6 Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(isoquinolin-- ylamino)gold complex ():... S6 Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-chloropyrimidin-- yl)amino)gold complex ():... S7 Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(diphenylamino)gold complex ():... S7 UV vis and fluorescence spectra:... S8 MR spectra... S9 DFT Calculations... S S

3 General considerations: Unless otherwise stated, all solvents and reagents were used as purchased and all reactions were performed under air. Deuterated solvents (e.g. CD Cl ) were filtered through basic alumina in order to remove traces of HCl. MR spectra were recorded on, and MHz spectrometers at room temperature in CD Cl. Chemical shifts ( ) are reported in ppm, relative to the solvent peaks (CDHCl,. ppm for H; CD Cl,.8 ppm for C). Data for H MR are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, sept = septuplet, br = broad signal, m = multiplet), coupling constants (J) in Hz and integration. For the assignment of the H and C{ H} MR spectra COSY, HSQC and HMBC experiments were also performed. Elemental analysis was carried out by the analytical services of London Metropolitan University. UV vis spectra were recorded in a Varian CaryWin Bio UV-Visible spectrophotometer at concentrations of ca.. mg/ml of complexes in CH Cl. Fluorescence spectra (λ max /excitation (nm) and λ max /emission (nm)) were recorded in a Cary Eclipse Fluorimeter (settings: nm excitation/emission slit, nm/min scan) at concentrations of ca. mg/ml of complexes in CH Cl. CCDC 99 (), 99 (), 99 (7), 99 (8), 99 (), 99 () and 996 () contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre (CCDC) via Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(phenylamino)gold Complex (): [(IPr)(OH)] ( mg, 66 µmol) and aniline (. mg, 66 µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The solvent was then concentrated under vacuum (until ca.. ml) and the product precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex was obtained as a white solid in 66% yield (7 mg). H MR ( MHz; CD Cl ): 7.7 (t, J = 7.8 Hz, H, CH p-ar ), 7.6 (d, J = 7.8 H Hz, H, CH m-ar ), 7. (s, H, CH imid. ), 6.6 (dd, J = 8., 7. Hz, H, ), 6. (tt, J = 7.,. Hz, H),.9 (dd, J = 8.,. Hz, H),. (bs, H),.6 (sept, J = 6.9 Hz, H),. (d, J = 6.9 Hz, H),. (d, J = 6.9 Hz, H). C{ H} MR ( MHz, CD Cl ): 7. (C carb ), 9. (C ), 6. (C o-ar ),. (C -Ar ),.7 (CH p-ar ),.7 (CH ),.6 (CH m-ar ),.8 (CH ),.69 (CH imid. ),.86 (CH ), 9.9 (CH ipr ),.6 (CH ),. (CH ). Anal. Calcd. for C H (677.67): C, 8.9; H, 6.;, 6.. Found: C, 8.; H, 6.;, 6.8. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(pyridin--ylamino)gold complex (): [(IPr)(OH)] ( mg, µmol) and -aminopyridine (.9 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex was obtained as a white solid in 9% yield ( mg). H MR ( MHz; CD Cl ): 7. (t, J = 7.8 Hz, H, CH p-ar + m, H, CH ), 7.6 (d, J = 7.8 Hz, H, CH m-ar ), 7. (s, H, CH imid. ), 6.7 (t, J = 8. Hz, H, CH ),.9 (m, H, CH ),.9 (d, J = 8. Hz, H, S

4 CH ),. (s, H, H),.6 (sept, J = 6.9 Hz, H, CH ipr ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR (6 MHz, CD Cl ): 79.6 (C carb ), (C ), 7.9 (CH ), H 6. (C o-ar ),.6 (CH ),.8 (C -Ar ),.76 (CH p-ar ),. (CH m-ar ),.9 (CH imid. ), 9.9 (CH ), 7.8 (CH ), 9.9 (CH ipr ),. (CH ),.9 (CH ). Anal. Calcd. for C H (678.66): C, 6.6; H, 6.9;, 8.6. Found: C, 6.; H, i.98;, 8.. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(pyridin--ylamino)gold Complex (): [(IPr)(OH)] ( mg, µmol) and -aminopyridine (.9 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex was obtained as a white solid in 8% yield (9 mg). H MR ( MHz; CD Cl ): 7.7 (t, J = 7.8 Hz, H, CH p-ar ), 7. (d, J =.9 H Hz, H, CH ), 7.6 (d, J = 7.9 Hz, H, CH m-ar ), 7.6 (dd, J =.,. Hz, H, CH ), 7. (s, H, CH imid. ), 6. (dd, J = 8.,. Hz, H, CH ), 6. (dd, J = 8.,.6 Hz, H, CH ),. (s, H, H),.6 (sept, J = 6.8 Hz, H, CH ipr ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR (6 MHz, CD Cl ): 79.8 (C carb ),. (C ), 6.8 (C o-ar ), 7.9 (CH ),.8 (C -Ar ),.7 (CH ),.79 (CH p-ar ),. (CH m-ar ),.7 (CH imid. ),. (CH ), 9.67 (CH ), 9. (CH ipr ),. (CH ).8 (CH ). Anal. Calcd. for C H (678.66): C, 6.6; H, 6.9;, 8.6. Found: C, 6.76; H,.98;, 8.6. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(pyridin--ylamino)gold complex (): [(IPr)(OH)] ( mg, µmol) and -aminopyridine (.9 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex 9a was obtained as a white solid in 88% yield ( mg). H MR ( MHz; CD Cl ): 7.8 (t, J = 7.8 Hz, H, CH p-ar ), 7. (bs, H, H CH ), 7.7 (d, J = 7.8 Hz, H, CH m-ar ), 7.6 (s, H, CH imid. ),.76 (bs, H, CH ),.89 (bs, H, H),.6 (sept, J = 6.9 Hz, H, CH ipr ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR ( MHz, CD Cl ): 79. (C carb ), 6. (C ), 8.8 (CH ), 6. (C o-ar ),.7 (C -Ar ),.8 (CH p-ar ),. (CH m-ar ),.6 (CH imid. ),.7 (CH ), 9. (CH ipr ),. (CH ),.8 (CH ). Anal. Calcd. for C H (678.66): C, 6.6; H, 6.9;, 8.6. Found: C, 6.8; H,.9;, 8.. S

5 Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-methylpyridin--yl)amino)gold Complex (6): [(IPr)(OH)] ( mg, µmol) and -amino--methylpyridine (.6 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex 6 was obtained as a white solid in 8% yield (8 mg). H MR ( MHz; CD Cl ): 7.7 (t, J = 7.8 Hz, H, CH p-ar ), 7.6 (d, J = H Hz, H, CH m-ar + H, CH ), 7. (s, H, CH imid. ), 6.6 (dd, J = 8.,. Hz, H, CH ),. (d, J = 8. Hz, H, CH ),.6 (bs, H, H),.6 (sept, J = 6.9 Hz, H, CH ipr ),.9 (s, H, CH 6 ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR ( MHz, CD Cl ): (C carb ), 67.8 (C ), 7. (CH ), 6. (CH o-ar ), 6.9 (CH ),.88 (CH -Ar ),.7 (CH p-ar ),. (CH m-ar ),. (CH imid. ),.79 (C ), 9.8 (CH ), 9. (CH ipr ),. (CH ),. (CH ), 7. (CH 6 ). Anal. Calcd. for C H (69.69): C, 7.; H, 6.6;, 8.9. Found: C, 7.8; H, 6.;, 8.. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-chloropyridin--yl)amino)gold complex (7): [(IPr)(OH)] ( mg, µmol) and -amino--chloropyridine (6.7 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex 7 was obtained as a white solid in 87% yield ( mg). H MR ( MHz; CD Cl ): 7.7 (t, J = 7.8 Hz, H, CH p-ar ), 7. (d, J =.7, Cl H Hz, H, CH ), 7.6 (d, J = 7.8 Hz, H, CH m-ar ), 7. (s, H, CH imid. ), 6.68 (dd, J = 9.,.7 Hz, H, CH ),.7 (d, J = 8.9 Hz, H, CH ),. (s, H, H),.6 (sept, J = 6.9 Hz, H, CH ipr ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR (6 MHz, CD Cl ): 79.6 (C carb ), 67.9 (C ), 6. (CH o- Ar),.7 (CH ),. (CH ),.76 (CH -Ar ),.8 (CH p-ar ),. (CH m-ar ),. (CH imid. ),.6 (C ),.96 (CH ), 9. (CH ipr ),. (CH ),.9 (CH ). Anal. Calcd. for C H Cl (7.): C,.9; H,.6;, Found: C,.8; H,.;, 7.9. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-(trifluoromethyl)pyridin-- yl)amino)gold complex (8): [(IPr)(OH)] ( mg, µmol) and -amino--(trifluoromethyl)pyridine (7. mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex 8 was obtained as a white solid in 7% yield (7 mg). H MR ( MHz; CD Cl ): 7.8 (s, H, CH ), 7.8 (t, J = 7.8 Hz, H, CH p-ar ), 7.7 (d, J = 7.8 Hz, H, CH m-ar ), 7.7 (s, H, CH imid. ), 6.9 (d, J = 8.7 Hz, H, CH ),. (d, J = 8.9 Hz, H, CH ),.67 (s, H, H),.6 (sept, J = 6.9 Hz, H, CH ipr ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). S

6 C{ H} MR ( MHz, CD Cl ): 78.7 (C carb ), 7.6 (C ), 6. (C o-ar ), 6. (q, J C-F =.9 Hz, CH ), 6.,.7 (C -Ar ),.8 (q, J C-F =.7 Hz, CH ),.88 (CH p-ar ), 6.9 (q, J C-F = 8.6 Hz, CF ),.7 (CH m-ar ),.66 (CH imid. ), 9. (q, J C-F =.6 Hz, C ), 9. (CH ), 9. (CH ipr ), H. (CH ),. (CH ). F 9 F{ C H} MR (76 MHz, CD Cl ): Anal. Calcd. for C H F (76.66): C,.8; H,.;, 7.. Found: C,.; H,.7;, 7.6. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-nitropyridin--yl)amino)gold complex (9): [(IPr)(OH)] ( mg, µmol) and -amino--nitropyridine (7. mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex 9 was obtained as a yellow solid in 8% yield ( mg). H MR ( MHz; CD Cl ): 8.9 (d, J =.7 Hz, H, CH ), 7.6 (t, J = 7.8 O H Hz, H, CH p-ar ), 7. (dd, J = 9.,.8 Hz, H, CH ), 7.8 (d, J = 7.8 Hz, H, CH m-ar ), 7.9 (s, H, CH imid. ),.9 (bs, H, H + d, J = 9. Hz, H, CH ),.9 (sept, J = 6.9 Hz, H, CH ipr ),. (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR (6 MHz, CD Cl ): 77. (C carb ), 7. (C ), 8.89 (CH ), 6. (C o-ar ),.8 (C -Ar ),.7 (C ),. (CH ),. (CH p-ar ),.6 (CH m-ar ),.87 (CH imid. ), 9. (CH ), 9. (CH ipr ),.8 (CH ),.8 (CH ). Anal. Calcd. for C H O (7.66): C,.; H,.7;, Found: C,.; H,.;, 9.6. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(isoquinolin--ylamino)gold complex (): [(IPr)(OH)] ( mg, µmol) and -aminoisoquinoline (7. mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex was obtained as a yellow solid in 8% yield ( mg). H MR ( MHz; CD Cl ): 8. (s, H, CH ), 7.6 (t, J = 7.8 Hz, H, H CH p-ar ), (d, J = 7.8 Hz, H, CH m-ar + m, H, CH isoquinoline ), 7. (s, H, CH imid. ), 7.7 (ddd, J = 8., 6.7,. Hz, H, CH isoquinoline ), 6.9 (d, J = 8. Hz, H, CH isoquinoline ), 6.7 (ddd, J = 8., 6.7,. Hz, H, CH isoquinoline ),.8 (m, H, CH ),. (s, H, H),.66 (7, J = 6.9 Hz, H, CH ipr ),.7 (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR (6 MHz, CD Cl ): (C carb ), 66.9 (C ),. (CH ), 6. (C o-ar ),. (C ),.9 (C -Ar ),.88 (CH p-ar ), 9. (CH isoquinoline ), 8.7 (CH isoquinoline ),.6 (CH m-ar ),.7 (CH isoquinoline ),. (CH imid. ),.7 (C ), 8.7 (CH isoquinoline ), 96.8 (CH ), 9. (CH ipr ),.9 (CH ),.8 (CH ). Anal. Calcd. for C 6 H (78.7): C, 9.; H,.9;, Found: C, 9.; H, 6.;, 7.6. S6

7 Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)((-chloropyrimidin-- yl)amino)gold complex (): [(IPr)(OH)] ( mg, µmol) and -chloropyrimidin--amine (6.7 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex was obtained as a white solid in 87% yield ( mg). H MR ( MHz; CD Cl ): (m, H, CH ), 7. (t, J = 7.8 Hz, H, Cl H CH p-ar ), 7. (d, J = 7.8 Hz, H, CH m-ar ), 7. (s, H, CH imid. ),. (s, H),.68-. (sept, J = 6.9 Hz, H, CH ipr ),.6 (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR (7 MHz, CD Cl ): 78. (C carb ), 7. (C ),.6 (CH ), 6. (C o-ar ),.8 (C -Ar ),.7 (CH p-ar ),.6 (CH m-ar ),.7 (CH imid. ),.68 (C ), 9. (CH ipr ),. (CH ),. (CH ). Anal. Calcd. for C H 9 Cl (7.9): C,.; H,.;, 9.8. Found: C,.6; H,.6;, 9.7. Synthesis of (,-bis(,6-diisopropylphenyl)imidazol--ylidene)(diphenylamino)gold complex (): [(IPr)(OH)] ( mg, µmol) and diphenylamine (8.8 mg, µmol) were dissolved in THF (. ml). The reaction mixture was stirred at room temperature for h. The product was then precipitated by addition of pentane ( ml), filtered, washed with more pentane ( ml) and dried under high vacuum. Complex was obtained as a yellow solid in 7% yield (8 mg). H MR ( MHz; CD Cl ): 7.6 (t, J = 7.8 Hz, H, CH p-ar ), 7.7 (d, J = 7.8 Hz, H, CH m-ar ), 7.7 (s, H, CH imid. ), (m, H, CH ), (m, H, CH ), 6. (tt, J = 7.,. Hz, H, CH ),.6 (sept, J = 6.9 Hz, H, CH ipr ),.6 (d, J = 6.9 Hz, H, CH ),. (d, J = 6.9 Hz, H, CH ). C{ H} MR ( MHz, CD Cl ): 78. (C carb ),.68 (C ), 6. (C o-ar ),.9 (C -Ar ),.7 (CH p-ar ), 8. (CH ),.6 (CH m-ar ),. (CH imid. ), 9.7 (CH ), 6.9 (CH ), 9. (CH ipr ),. (CH ),. (CH ). Anal. Calcd. for C 9 H 6 (7.77): C, 6.; H, 6.;,.7. Found: C, 6.; H, 6.9;,.68. S7

8 Intensity (AU) Absorbance (AU) UV vis and fluorescence spectra: Equipment Used: UV: Varian CaryWin Bio UV Vis spectrophotometer Fluorescence: Cary Eclipse Fluorimeter (settings: nm excitation/emission slit, nm/min scan).. H Exc Emis 6 6 S8

9 Intensity (AU) Absorbance (AU) H 8 6 Exc Emis 6 6 S9

10 Intensity (AU) Absorbance (AU).8.6. H Exc Emis 6 6 S

11 Intensity (AU) Absorbance (AU). H Exc Emis S

12 Intensity (AU) Absorbance (AU).. H Exc Emis 6 S

13 Intensity (AU) Absorbance (AU).. Cl H Exc Emis 6 6 S

14 Intensity (AU) Absorbance (AU).. H.8.6 F C Exc Emis 6 6 S

15 Intensity (AU) Absorbance (AU).8.6. H. O Exc Emis S

16 Intensity (AU) Absorbance (AU).. H Exc Emis 6 6 S6

17 Intensity (AU) Absorbance (AU). H. Cl Exc Emis 6 S7

18 Intensity (AU) Absorbance (AU) Exc Emis 6 6 S8

19 MR Spectra H S9

20 H S

21 H S

22 H S

23 6 H S

24 Cl H S

25 F C H S

26 S f(pm) cdcl.cdcl.cdcl H O

27 S f(pm) hdo cdcl.cdcl.cdcl H

28 Cl H S8

29 S9

30 DFT Calculations Calculations were performed at the M6-L/SDD level of theory using Gaussian 9.[] The crystal structure of was used as the starting point for optimization. The structure was then optimized using tight convergence criteria and the ultrafine grid. The resulting structure was confirmed to be a minimum via frequency calculations (no imaginary frequencies). The co-ordinates are listed below. [] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, T. Vreven, K.. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani,. Rega, G. A. Petersson, H. akatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. akajima, Y. Honda, O. Kitao, H. akai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. stin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. anayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez and J. A. Pople, Gaussian, Revision D., Gaussian Inc., Wallingford, CT, C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H H H H H H H H.8.. H S

31 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S