Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

Transcription

1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

2 Electronic Perturbation in a Molecular Wire of [IrCl 5 (NO)] Units Florencia Di Salvo, [a] Natalia Escola, [a] Damián A. Scherlis,* [a] Darío A. Estrin, [a] Carlos Bondía, [b] Daniel Murgida, [b] José M. Ramallo López, [c] Félix G. Requejo, [c] Linda Shimon, [d] and Fabio Doctorovich* [a] [a] F. Di Salvo, Dr. N. Escola, Dr. D. A. Scherlis, Prof. D. A. Estrin, Prof. F. Doctorovich Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, piso 3, C1428EHA BuenosAires. Fax: (+5411) F. D. : doctorovich@qi.fcen.uba.ar D. A. S. : damian@qi.fcen.uba.ar [b] Dr. C. Bondía, Dr. D. Murgida Department Max Volmer Laboratory of Biophysical Chemistry, Institute of Chemistry, Technical University of Berlin Institution, Strasse des 17. Juni 135, D Berlin, Germany. [c] Dr. J. M. Ramallo López, Dr. F. G. Requejo INIFTA IFLP (CONICET) and Departamento de Física, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 1900 La Plata, Argentina. [d] Dr. L. Shimon Department of Chemical Services, The Weizmann Institute of Science, Rehovot 76100, Israel. 1

3 Resonance Raman Measurements. a b1 b2 2.5 mm 2.5 mm 500 µm Figure S1: crystals used in Resonace Raman Experiments. a. K[IrCl 5 (NO)]. b1 and b2. AsPh 4 [IrCl 5 (NO)]. Raman shift / cm Polynomial Regression for Data3_D: Y = A + B1*X + B2*X^2 Weight given by Data3_C error bars. Parameter Value Error A B B E E-6 R-Square(COD) SD N P < Linear Regression for Data3_D: Y = A + B * X Parameter Value Error A B E-4 R SD N P < a K IrCl 5 NO λ exc = 514,5 nm (600 µw) T / K Raman shift / cm Polynomial Regression for Data2_C: Y = A + B1*X + B2*X^2 Parameter Value Error A B B E E-5 R-Square(COD) SD N P < b Linear Regression for Data2_C: Y = A + B * X Parameter Value Error A B R SD N P < AsPh 4 IrCl 5 NO λ exc = 514,5 nm (600 µw) T / K Figure S2: influence of the temperature in Resonance Raman Shift. a. K[IrCl 5 (NO)]. b. AsPh 4 [IrCl 5 (NO)]. IR correlation K[IrCl 5 (NO)] nno [cm -1 ] Na[IrCl 5 (NO)] y = x R 2 = PPh 4 [IrCl 5 (NO)] d NO [?] Figure S3. FTIR solid state d NO vs ν NO correlation (red line) for K[IrCl 5 (NO)], Na[IrCl 5 (NO)] and PPh 4 [IrCl 5 (NO)]. 2

4 Summarized Structural Results. Table S1. Selected structural parameters for PPh 4 [IrCl 5 (NO)]. Technique ClIrN IrNO d N-O d Ir-N d Ir-O d Ir-Cl(trans) d Ir-Cl(eq.) X-ray (3) 149.3(7) 1.195(18) 1.740(14) 2.841(32) 2.264(2) (11) DFT (solid state) EXAFS ± ± ± ± 0.01 DFT (vacuo) [a] [a] Optimization of one IrCl 5 (NO] unit performed in a background of NPA calculated charges, located between two IrCl 5 (NO] units and twelve counterions, all of them located as in the X-ray PPh + 4 structure. EXAFS and XANES Measurements. Normalized absorption / a.u. K[IrCl 5 (NO)] PPh 4 [IrCl 5 (NO)] Energy / kev Figure S4. XANES spectra at the Ir L 2 edge showing that the intensity of the white line is exactly the same for both samples. 3

5 FT Amplitude (U.A.) a EXAFS Fit X-ray isotr b Distance Fit (Å) X-ray value (Å) d(irn) 1.78± d(iro) 2.93± d(ircl trans ) 2.3± d(ircl eq ) 2.34± R [Å] Figure S5: EXAFS results for PPh 4 [IrCl 5 (NO)] considering the X-ray structure (isotropic refinement) as data input for the simulation. a. Fourier transform amplitude of the EXAFS spectrum (blue dots) and the obtained fit (full red line). b. Obtained values. Table S2. EXAFS fit results for PPh 4 [IrCl 5 (NO)] (DFT solid state geometry as data input) Atom N* D [Å] s 2 x 10 3 [Å -2 ] E 0 [ev] N ± ± ± 1 Cl trans ± ± ± 1 Cl eq ± ± ± 1 O ± ± ± 1 * The coordination number for every shell was fixed for the fit Table S3. EXAFS fit results for K[IrCl 5 (NO)] Atom N* D [Å] s 2 x 10 3 [Å -2 ] E 0 [ev] N ± ± ± 1 Cl trans ± ± ± 1 Cl eq ± ± ± 1 Cl eq ± ± ± 1 O ± ± ± 1 * The coordination number for every shell was fixed for the fit 4

6 FT Amplitude [A. U.] R [Å] Figure S6. Fourier transform amplitude of the EXAFS spectrum for K[IrCl 5 (NO)] (dots) and the obtained fit (full line). Magnetic Measurements. a b Figure S7. χ(t) behaviour from SQUID measurements. a. PPh 4 + salt. b. K + salt. EPR Spectroscopy. The EPR spectra were recorded at (25±1) C and 9.8 GHz (X Band) in an ER-200 spectrometer (Bruker Analytische Messtechnik GMBH, Karlsruhe, Germany). The samples were placed in glass capillaries (1 mm i.d.), sealed at both ends and housed in 4-mm quartz tubes containing silicone oil for maintaining temperature uniformity. Field modulation frequency was 100 KHz, and its amplitude was well below 30% of the minor linewidths in each case, to avoid spectral shape distortions 5

7 X-ray diffraction studies. Figure S8. X-ray structure for the anion portion of PPh 4 [IrCl 5 (NO)] (isotropic refinement). Thermal ellipsoids are drawn at the 50% level. (All the equivalent oxygen atoms are shown) Figure S9: X-ray structure for the anion portion of PPh 4 [IrCl 5 (NO)] (anisotropic refinement). Thermal ellipsoids are drawn at the 50% level. (Only one of the four equivalent oxygen atoms is shown) 0 As N a Cl 2 Ir Cl 2 Cl 1 b c Figure S10: X-ray structure of AsPh 4 [IrCl 5 (NO)]; thermal ellipsoids are drawn at the 50% level. a. Stoichiometric fragment. b. View of a extended cell normal to (001). c. View of a extended cell normal to (100). 6

8 DFT Calculations. Figure S11: Difference electron density map for the X-ray structure of PPh 4 [IrCl 5 (NO)] (isotropic refinement). The arrow shows that there is no residual density close to the N atom. 7

9 Table S4: Calculated energy differences from singlet to triplet systems. System DE (kcal/mol) [IrCl 5 NO] (CSS/opt) [IrCl 5 NO] (OST/opt) 18.8 [IrCl 5 NO] (CSS/opt.) [IrCl 5 NO] (OSS/SP) 14.7 [IrCl 5 NO] (from X ray PPh 4 geometry) (CSS/SP) (OST/SP) 16.3 [IrCl 5 NO] (from X ray Na geometry) (CSS/SP) (OST/SP) 40.6 Figure S12: Spin density resulted from DFT single Figure S13: [IrCl 5 (NO)] optimized structure in vacuo point calculation of the OSS [IrCl 5 (NO)] Figure S14: Optimization of one IrCl 5 (NO] unit performed in a background of NPA calculated charges, located between two [IrCl 5 (NO)] units and twelve counterions, all of them located as in the X-ray PPh 4 + structure 8

10 (A) (B) (C) Figure S15. Calculated MO for [IrCl 5 (NO)]. (A) HOMO, (B) and (C) LUMO for the optimized structure in vacuo. Figure S16. Electronic spin density for the X-ray structure of PPh 4 [IrCl 5 (NO)] (isotropic refinement), calculated by DFT in the solid state. Blue and red lobes represent unpaired electron density of opposite spin. xyz of the presented structures Optimized IrCl 5 (NO)] BPW91 O N Ir Cl Cl Cl Cl Cl

11 B3LYP O Ir N Cl Cl Cl Cl Cl Optimized IrCl 5 (NO)] 2 BPW91 O Ir N Cl Cl Cl Cl Cl B3LYP O Ir N Cl Cl Cl Cl Cl Optimized IrCl 5 (NO)] dimer 10

12 BPW91 (similar results for B3LYP) Ir Ir Cl Cl Cl Cl Cl Cl Cl Cl Cl N O Cl N O Open Shell structure of IrCl 5 (NO)] BPW91 (similar results for B3LYP) O N Ir Cl Cl Cl Cl Cl Partially optimized IrCl 5 (NO)] in a background of charges BPW91 (similar results for B3LYP) O N

13 Ir Cl Cl Cl Cl Cl Partially optimized IrCl 5 (NO)] in solid state, ( Coordinates of the unit cell). Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl H H H H H H H H H H H H H H H

14 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 C C C C C C C C C C

15 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 C C C

16 C C C N N O O P P Ir Ir Complete References. (34) M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, 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. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople. Gaussian 98, ReV. A7; Gaussian, Inc., Pittsburgh, PA,

17 CHECKCIF Reports of the X-ray diffraction structures. checkcif/platon report (basic structural check) No syntax errors found. Datablock: m515b (CSD ) Bond precision: O- N = A Wavelength= Cell: a=22.366(5) b=6.8800(14) c=5.9910(12) alpha=90 beta=90 gamma=90 Calculated Reported Volume 921.9(3) 921.9(3) Space group P n m a Pnma Hall group -P 2ac 2n? Moiety formula Cl5 Ir N O, Cl, Na? Sum formula Cl6 Ir N Na O Cl6 Ir N Na O Mr Dx,g cm Z 4 4 Mu (mm-1) F F000' h,k,lmax 29,8,7 28,8,7 Nref Tmin,Tmax 0.156, ,0.294 Tmin' Correction method= 'EMPIRICAL' Data completeness= Ratio = Theta(max)= R(reflections)= ( 1005) wr2(reflections)= ( 1132) S = Npar= 55 The following ALERTS were generated. Each ALERT has the format test-name_alert_alert-type_alert-level. 16

18 Click on the hyperlinks for more details of the test. Alert level A PLAT078_ALERT_1_A No H-atoms, but _solution_hydrogens reported as PLAT079_ALERT_1_A No H-atoms, but _hydrogen_treatment reported as geom mixed Alert level C ABSTY02_ALERT_1_C An _exptl_absorpt_correction_type has been given without a literature citation. This should be contained in the _exptl_absorpt_process_details field. Absorption correction given as empirical PLAT030_ALERT_1_C _diffrn_reflns_number.le. _reflns_number_total? PLAT062_ALERT_4_C Rescale T(min) & T(max) by PLAT431_ALERT_2_C Short Inter HL..A Contact Cl2.. O Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Cl2.. N Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Cl3.. O Ang. PLAT431_ALERT_2_C Short Inter HL..A Contact Cl3.. O Ang. PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 1 CL2 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 2 CL1 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 3 CL1 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 4 CL3 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 5 CL3 -IR1 -N1 -O PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 Cl PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 Na Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be 17

19 replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported Tmax scaled Tmin scaled ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 14 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 8 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check 18

20 PLATON version of 14/11/2006; check.def file version of 13/11/2006 Datablock m515a - ellipsoid plot 19

21 checkcif/platon report (basic structural check) No syntax errors found. Datablock: m420iso (CSD ) Bond precision: C-C = A Wavelength= Cell: a= (2) b= (2) c=7.8070(2) alpha=90 beta=90 gamma=90 Calculated Reported Volume (4) (4) Space group P 4/n P4/n Hall group -P 4a? Moiety formula C24 H20 P, Cl5 Ir N O? Sum formula C24 H20 Cl5 Ir N O P C24 H20 Cl5 Ir N O P Mr Dx,g cm Z 2 2 Mu (mm-1) F F000' h,k,lmax 16,16,10 16,11,10 Nref Tmin,Tmax 0.713, ,0.760 Tmin' Correction method= 'EMPIRICAL' Data completeness= Ratio = Theta(max)= R(reflections)= ( 1449) wr2(reflections)= ( 1484) S = Npar= 78 The following ALERTS were generated. Each ALERT has the format test-name_alert_alert-type_alert-level. Click on the hyperlinks for more details of the test. 20

22 Alert level B PLAT431_ALERT_2_B Short Inter HL..A Contact Cl2.. O1A Ang. PLAT431_ALERT_2_B Short Inter HL..A Contact Cl2.. O1A Ang. PLAT431_ALERT_2_B Short Inter HL..A Contact Cl2.. O1A Ang. PLAT431_ALERT_2_B Short Inter HL..A Contact Cl2.. O1A Ang. Alert level C ABSTY02_ALERT_1_C An _exptl_absorpt_correction_type has been given without a literature citation. This should be contained in the _exptl_absorpt_process_details field. Absorption correction given as empirical PLAT062_ALERT_4_C Rescale T(min) & T(max) by PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT202_ALERT_3_C Isotropic non-h Atoms in Anion/Solvent... 1 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for N1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Ir1 PLAT302_ALERT_4_C Anion/Solvent Disorder Perc. PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 15 CL2 -IR1 -N1 -O1A PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 20 CL2 -IR1 -N1 -O1A PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 25 CL2 -IR1 -N1 -O1A PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 30 CL2 -IR1 -N1 -O1A PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1A -N1 -O1A PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1A -N1 -O1A PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1A -N1 -O1A PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1A -N1 -O1A PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1A -O1A -O1A PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1A -O1A -O1A Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values 21

23 From the CIF: _diffrn_reflns_theta_max From the CIF: _reflns_number_total 1484 From the CIF: _diffrn_reflns_limit_ max hkl From the CIF: _diffrn_reflns_limit_ min hkl TEST1: Expected hkl limits for theta max Calculated maximum hkl Calculated minimum hkl ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 18 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 9 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check PLATON version of 14/11/2006; check.def file version of 13/11/2006 Datablock m420iso - ellipsoid plot 22

24 checkcif/platon report (basic structural check) No syntax errors found. Datablock: m559_1a (CSD ) Bond precision: C-C = A Wavelength= Cell: a= (18) b= (18) c=7.8830(16) alpha=90 beta=90 gamma=90 Calculated Reported Volume (4) (4) 23

25 Space group P 4/n P4/n Hall group -P 4a? Moiety formula C24 H20 As, Cl5 Ir N O? Sum formula C24 H20 As Cl5 Ir N O C24 H20 As Cl5 Ir N O Mr Dx,g cm Z 2 2 Mu (mm-1) F F000' h,k,lmax 16,16,10 11,16,10 Nref Tmin,Tmax 0.043, ,0.337 Tmin' Correction method= 'EMPIRICAL' Data completeness= Ratio = Theta(max)= R(reflections)= ( 1392) wr2(reflections)= ( 1487) S = Npar= 79 The following ALERTS were generated. Each ALERT has the format test-name_alert_alert-type_alert-level. Click on the hyperlinks for more details of the test. Alert level A ABSTM02_ALERT_3_A Crystal and compound unsuitable for non-numerical corrections. Product of mu and tmid > 3.0 Value of mu given = tmid = PLAT060_ALERT_3_A Ratio Tmax/Tmin (Exp-to-Rep) (too) Large PLAT065_ALERT_3_A Crystal Requires Numerical Correction mu*tmid Alert level B PLAT431_ALERT_2_B Short Inter HL..A Contact Cl1.. O Ang. PLAT431_ALERT_2_B Short Inter HL..A Contact Cl1.. O Ang. PLAT431_ALERT_2_B Short Inter HL..A Contact Cl1.. O Ang. PLAT431_ALERT_2_B Short Inter HL..A Contact Cl1.. O Ang. 24

26 Alert level C ABSTY02_ALERT_1_C An _exptl_absorpt_correction_type has been given without a literature citation. This should be contained in the _exptl_absorpt_process_details field. Absorption correction given as empirical PLAT030_ALERT_1_C _diffrn_reflns_number.le. _reflns_number_total? PLAT062_ALERT_4_C Rescale T(min) & T(max) by PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for N1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Ir1 PLAT302_ALERT_4_C Anion/Solvent Disorder Perc. PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 1 CL1 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 6 CL1 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 11 CL1 -IR1 -N1 -O PLAT710_ALERT_4_C Delete or Linear Torsion Angle... # 16 CL1 -IR1 -N1 -O PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1 -N1 -O PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1 -N1 -O PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1 -N1 -O PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF Deg. O1 -N1 -O PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C24 H20 As Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max From the CIF: _reflns_number_total 1487 From the CIF: _diffrn_reflns_limit_ max hkl From the CIF: _diffrn_reflns_limit_ min hkl TEST1: Expected hkl limits for theta max Calculated maximum hkl Calculated minimum hkl ALERT level A = In general: serious problem 25

27 4 ALERT level B = Potentially serious problem 17 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 10 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check 26

28 PLATON version of 14/11/2006; check.def file version of 13/11/2006 Datablock m559_1a - ellipsoid plot 27