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_1529427
_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         'C52 H36 N6 O4, 0.595(C H2 Cl2)'
_chemical_formula_sum            'C52.59 H37.19 Cl1.19 N6 O4'
_chemical_formula_weight         859.29
_chemical_name_systematic
'5-[4-[(2-methoxy-4-nitro-phenylcarbonyl)-amino]phenyl]-10,15,20-triphenyl porphyrin'
_chemical_properties_physical    Photo-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_Hall           '-F 2uv 2vw'
_space_group_name_H-M_alt        'F d d d'
_symmetry_space_group_name_Hall  '-F 2uv 2vw'
_symmetry_space_group_name_H-M   'F d d d :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_audit_update_record
;
2015-06-10 deposited with the CCDC.
2015-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            32
_cell_length_a                   23.5964(4)
_cell_length_b                   37.3470(6)
_cell_length_c                   40.0789(6)
_cell_measurement_reflns_used    9536
_cell_measurement_temperature    110.00(10)
_cell_measurement_theta_max      27.2710
_cell_measurement_theta_min      3.0500
_cell_volume                     35319.7(10)
_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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      110.00(10)
_diffrn_detector_area_resol_mean 16.1450
_diffrn_measured_fraction_theta_full 0.9972
_diffrn_measured_fraction_theta_max 0.9972
_diffrn_measurement_details
;
  1 omega  -35.00   36.25   0.7500   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7020   77.0000 -180.0000 95

  2 omega   -2.00   48.25   0.7500   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7020   77.0000  -90.0000 67

  3 omega   37.00   63.25   0.7500   85.0000
omega____ theta____ kappa____ phi______ frames
    -       22.0301   77.0000  -30.0000 35

  4 omega  -93.00  -31.50   0.7500   85.0000
omega____ theta____ kappa____ phi______ frames
    -      -20.7020  -57.0000 -180.0000 82
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0059453000
_diffrn_orient_matrix_UB_12      -0.0097095000
_diffrn_orient_matrix_UB_13      -0.0148073000
_diffrn_orient_matrix_UB_21      -0.0285557000
_diffrn_orient_matrix_UB_22      0.0059084000
_diffrn_orient_matrix_UB_23      0.0006104000
_diffrn_orient_matrix_UB_31      0.0072757000
_diffrn_orient_matrix_UB_32      0.0152139000
_diffrn_orient_matrix_UB_33      -0.0096737000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            26924
_diffrn_reflns_theta_full        25.35
_diffrn_reflns_theta_max         25.35
_diffrn_reflns_theta_min         2.88
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.152
_exptl_absorpt_correction_T_max  0.998
_exptl_absorpt_correction_T_min  0.997
_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 blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             14303.400
_exptl_crystal_size_max          0.1818
_exptl_crystal_size_mid          0.1617
_exptl_crystal_size_min          0.1159
_refine_diff_density_max         0.849
_refine_diff_density_min         -1.069
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     606
_refine_ls_number_reflns         8081
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0578
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0809P)^2^+167.7597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1587
_refine_ls_wR_factor_ref         0.1693
_reflns_number_gt                6545
_reflns_number_total             8081
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5sc02099a2.cif
_cod_data_source_block           rnp1302
_cod_depositor_comments
'Adding full bibliography for 1529427--1529428.cif.'
_cod_original_cell_volume        35319.7(9)
_cod_database_code               1529427
_chemical_oxdiff_formula         'C52 H36 N6 O4'
_chemical_oxdiff_usercomment     'Christopher TPPMBNO2'
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H53A,H53B} of C53, H50 of C50, H51 of C51, H3 of C3, H2 of C2, {H54A,H54B}
  of C54, {H53C,H53D} of C53A, H26 of C26, H25 of C25, H24 of C24, H23 of C23,
  H22 of C22, H18 of C18, H17 of C17, H13 of C13, H12 of C12, H8 of C8, H7 of
  C7, H29 of C29, H28 of C28, H30 of C30, H31 of C31, H32 of C32, H34 of C34,
  H35 of C35, H36 of C36, H37 of C37, H38 of C38, H40 of C40, H41 of C41, H43
  of C43, H44 of C44, H48 of C48
 At 1.5 times of:
  {H52A,H52B,H52C} of C52
2. Uiso/Uaniso restraints and constraints
Uanis(C54) ~ Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
3. Others
 Sof(C53)=Sof(H53A)=Sof(H53B)=1-Sof(H53A)=1-Sof(H53A)=1-Sof(H53A)
 Fixed Sof: C54(0.09375) H54A(0.09375) H54B(0.09375) Cl2(0.1875)
4.a Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C53A(H53C,H53D), C54(H54A,H54B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18),
 C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30),
  C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38),
 C40(H40), C41(H41), C43(H43), C44(H44), C48(H48), C50(H50), C51(H51)
4.c Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C)
;