Comparison of rhenium‒porphyrin dyads for CO2photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy
Windle, Christopher D.; George, Michael W.; Perutz, Robin N.; Summers, Peter A.; Sun, Xue Zhong; Whitwood, Adrian C.; Chem. Sci. 6 (2015) 6847–; doi:10.1039/C5SC02099A

data_1529428
_publ_section_title
;
 Comparison of rhenium--porphyrin dyads for CO2photoreduction:
 photocatalytic studies and charge separation dynamics studied by
 time-resolved IR spectroscopy
;
_journal_issue                   12
_journal_name_full               'Chem. Sci.'
_journal_page_first              6847
_journal_paper_doi               10.1039/C5SC02099A
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety
'C65 H44 N8 O4 Re Zn, 2(F3 P0.5), 2.5(C H2 Cl2)'
_chemical_formula_sum            'C67.5 H49 Cl5 F6 N8 O4 P Re Zn'
_chemical_formula_weight         1609.93
_chemical_name_systematic
'5-{4-[Rhenium(I)tricarbonyl(3-picoline)-4-methyl-2,2?-bipyridine- 4?-carboxyamidyl]phenyl}-10,15,20-triphenylporphyrinatozinc(II) hexafluorophosphate'
_chemical_properties_physical    Photo-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-06-10 deposited with the CCDC.
2015-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                98.752(3)
_cell_angle_beta                 92.264(3)
_cell_angle_gamma                106.821(3)
_cell_formula_units_Z            2
_cell_length_a                   12.9474(5)
_cell_length_b                   15.8804(5)
_cell_length_c                   17.3277(6)
_cell_measurement_reflns_used    9679
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      29.6540
_cell_measurement_theta_min      3.2910
_cell_volume                     3357.4(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega    2.00   92.00   1.0000   65.0000
omega____ theta____ kappa____ phi______ frames
    -       22.9865   57.0000  -90.0000 90

  2 omega   25.00   69.00   1.0000   65.0000
omega____ theta____ kappa____ phi______ frames
    -       22.9865 -107.0000  143.0000 44

  3 omega   -7.00   49.00   1.0000   65.0000
omega____ theta____ kappa____ phi______ frames
    -       22.9865   77.0000    0.0000 56

  4 omega  -43.00   36.00   1.0000   65.0000
omega____ theta____ kappa____ phi______ frames
    -       22.9865  -57.0000   30.0000 79

  5 omega  -17.00   96.00   1.0000   65.0000
omega____ theta____ kappa____ phi______ frames
    -       22.9865   19.0000 -150.0000 113
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0066577000
_diffrn_orient_matrix_UB_12      0.0061564000
_diffrn_orient_matrix_UB_13      -0.0393976000
_diffrn_orient_matrix_UB_21      -0.0570231000
_diffrn_orient_matrix_UB_22      -0.0153352000
_diffrn_orient_matrix_UB_23      -0.0087021000
_diffrn_orient_matrix_UB_31      -0.0022886000
_diffrn_orient_matrix_UB_32      0.0443829000
_diffrn_orient_matrix_UB_33      0.0100463000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25307
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         2.846
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.452
_exptl_absorpt_correction_T_max  0.838
_exptl_absorpt_correction_T_min  0.732
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_F_000             1602
_exptl_crystal_size_max          0.1612
_exptl_crystal_size_mid          0.091
_exptl_crystal_size_min          0.0831
_refine_diff_density_max         4.118
_refine_diff_density_min         -1.780
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     880
_refine_ls_number_reflns         14802
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0809
_refine_ls_R_factor_gt           0.0659
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1209P)^2^+7.5250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1868
_refine_ls_wR_factor_ref         0.1986
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12030
_reflns_number_total             14802
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc02099a2.cif
_cod_data_source_block           rnp1309
_cod_depositor_comments
'Adding full bibliography for 1529427--1529428.cif.'
_cod_original_formula_sum        'C67.50 H49 Cl5 F6 N8 O4 P Re Zn'
_cod_database_code               1529428
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C67.5 H49 Cl5 F6 N8 O4 P1 Re1 Zn1'
_chemical_oxdiff_usercomment     'Christopher DYAD1'
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P2-F4 = P2-F5 = P2-F6 = P2-F7 = P2-F8 = P2-F9
 1.6 with sigma of 0.005
 C52A-C52
 1 with sigma of 0.02
 Cl5-C70 \\sim C70-Cl6
 with sigma of 0.02
 F4-F5 \\sim F4-F6 \\sim F4-F7 \\sim F4-F8
 with sigma of 0.005
 F9-F5 \\sim F9-F6 \\sim F9-F7 \\sim F9-F8
 with sigma of 0.005
 F5-F6 \\sim F6-F7 \\sim F7-F8 \\sim F8-F5
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(F5) = Uanis(F7)
Uanis(F4) = Uanis(F9)
Uanis(F6) = Uanis(F8)
Uanis(C53) = Uanis(C53A)
Uanis(C52) = Uanis(C52A)
Uanis(C51) = Uanis(C51A)
Uanis(C50) = Uanis(C50A)
Uanis(C48) = Uanis(C48A)
Uanis(C49) = Uanis(C49A)
4. Others
 Sof(C48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=
 Sof(C52A)=Sof(H52A)=Sof(C53A)=Sof(H53A)=1-FVAR(1)
 Sof(C48)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=
 Sof(H52)=Sof(C53)=Sof(H53)=FVAR(1)
 Fixed Sof: C70(0.5) H70A(0.5) H70B(0.5) Cl5(0.5) Cl6(0.5) F4(0.5) F5(0.5)
 F6(0.5) F7(0.5) F8(0.5) F9(0.5) P2(0.5)
5.a Riding coordinates:
 N4(H4A)
5.b Secondary CH2 refined with riding coordinates:
 C66(H66A,H66B), C70(H70A,H70B), C67(H67A,H67B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14),
 C15(H15), C17(H17), C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31),
  C35(H35), C36(H36), C40(H40), C41(H41), C45(H45), C46(H46), C49A(H49A),
 C50A(H50A), C51A(H51A), C52A(H52A), C53A(H53A), C49(H49), C50(H50), C51(H51),
 C52(H52), C53(H53), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61),
  C62(H62), C63(H63), C64(H64), C65(H65)
5.d Fitted hexagon refined as free rotating group:
 C48A(C49A,C50A,C51A,C52A,C53A)
5.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C18(H18A,H18B,H18C)
;
_olex2_date_sample_data_collection 2013-03-05
_olex2_submission_special_instructions 'No special instructions were received'