Structure-activity relationships in well-defined conjugated oligomer photocatalysts for hydrogen production from water
Aitchison, Catherine M.; Sachs, Michael; Little, Marc; Wilbraham, Liam; Brownbill, Nick J.; Kane, Chris; Blanc, Frédéric; Zwijnenburg, Martijn; Durrant, James; Sprick, Reiner Sebastian; Cooper, Andrew; Chemical Science  (2020) –; doi:10.1039/D0SC02675A

data_1558681
_publ_section_title
;
 Structure-activity relationships in well-defined conjugated oligomer
 photocatalysts for hydrogen production from water
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02675A
_journal_year                    2020
_chemical_formula_moiety         'C45 H38'
_chemical_formula_sum            'C45 H38'
_chemical_formula_weight         578.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-03-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-04-28 deposited with the CCDC.	2020-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.790(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.5956(5)
_cell_length_b                   22.8016(4)
_cell_length_c                   16.5804(4)
_cell_measurement_reflns_used    39312
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      24.4000
_cell_measurement_theta_min      1.7560
_cell_volume                     6970.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection
'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -100.00  25.00   1.00   40.00    --  -10.00 -68.00   0.00  125
  2  \w   -100.00  25.00   1.00   40.00    --  -10.00 -68.00 120.00  125
  3  \w   -100.00  25.00   1.00   40.00    --  -10.00 -68.00 240.00  125
  4  \w   -100.00  25.00   1.00   40.00    --  -10.00 -30.00  90.00  125
  5  \w   -100.00  25.00   1.00   40.00    --  -10.00 -30.00 210.00  125
  6  \w    -90.00  90.00   1.00   40.00    --    0.00   0.00   0.00  180
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0081109000
_diffrn_orient_matrix_UB_12      0.0011211000
_diffrn_orient_matrix_UB_13      -0.0385332000
_diffrn_orient_matrix_UB_21      -0.0373565000
_diffrn_orient_matrix_UB_22      -0.0032971000
_diffrn_orient_matrix_UB_23      -0.0240293000
_diffrn_orient_matrix_UB_31      -0.0042765000
_diffrn_orient_matrix_UB_32      0.0309314000
_diffrn_orient_matrix_UB_33      -0.0012287000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0544
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            145548
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.383
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.062
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65450
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.103
_exptl_crystal_description       plate
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.412
_exptl_crystal_size_mid          0.293
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.693
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.572
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1077
_refine_ls_number_reflns         14055
_refine_ls_number_restraints     1309
_refine_ls_restrained_S_all      1.554
_refine_ls_R_factor_all          0.1680
_refine_ls_R_factor_gt           0.0955
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0900P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2331
_refine_ls_wR_factor_ref         0.2548
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7267
_reflns_number_total             14055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02675a3.cif
_cod_data_source_block           MeF3_298K_publ
_cod_database_code               1558681
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.975
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C46A-C59A = C59B-C46B = C59A-C52A = C53B-C59B = C74A-C63A = C65B-C74B = C74B-
 C72B = C68A-C74A = C80B-C89B = C82B-C89B = C89A-C78A = C89A-C82A = C13-C1 =
 C13-C7 = C29-C18 = C23-C29
 1.53 with sigma of 0.02
 C58A-C59A = C58B-C59B = C60A-C59A = C59B-C60B = C75B-C74B = C75A-C74A = C73B-
 C74B = C73A-C74A = C88A-C89A = C90A-C89A = C89B-C90B
 1.54 with sigma of 0.02
 C52B-C47B = C47A-C53A = C67A-C64A = C64B-C67B = C83B-C79B = C79A-C87A = C8-C2
 = C19-C22
 1.46 with sigma of 0.02
 C76B-C70B = C70A-C76A
 1.49 with sigma of 0.01
 C15-C13 = C14-C13 = C29-C30 = C29-C28
 1.54 with sigma of 0.02
 C89B-C88B
 1.54 with sigma of 0.02
3. Restrained planarity
 C76B, C77B, C78B, C79B, C80B, C81B, C82B, C83B, C84B, C85B, C86B, C87B, C89B
 with sigma of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C76A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C47A(0.5) C46A(0.5) C51A(0.5) H51A(0.5) C50A(0.5) H50A(0.5)
 C49A(0.5) H49A(0.5) C48A(0.5) H48A(0.5) C56A(0.5) C57A(0.5) H57A(0.5)
 C52A(0.5) C53A(0.5) C54A(0.5) H54A(0.5) C55A(0.5) H55A(0.5) C58A(0.5)
 H58A(0.5) H58B(0.5) H58C(0.5) C59A(0.5) C60A(0.5) H60A(0.5) H60B(0.5)
 H60C(0.5) C63A(0.5) C64A(0.5) C65A(0.5) H65A(0.5) C66A(0.5) H66A(0.5)
 C61A(0.5) C62A(0.5) H62A(0.5) C68A(0.5) C69A(0.5) H69A(0.5) C70A(0.5)
 C71A(0.5) H71A(0.5) C72A(0.5) H72A(0.5) C67A(0.5) C73A(0.5) H73A(0.5)
 H73B(0.5) H73C(0.5) C74A(0.5) C75A(0.5) H75A(0.5) H75B(0.5) H75C(0.5)
 C76A(0.5) C81A(0.5) H81A(0.5) C80A(0.5) H80A(0.5) C79A(0.5) C78A(0.5)
 C77A(0.5) H77A(0.5) C87A(0.5) C86A(0.5) H86A(0.5) C85A(0.5) H85A(0.5)
 C84A(0.5) H84A(0.5) C83A(0.5) H83A(0.5) C82A(0.5) C88A(0.5) H88A(0.5)
 H88B(0.5) H88C(0.5) C89A(0.5) C90A(0.5) H90A(0.5) H90B(0.5) H90C(0.5)
 C47B(0.5) C46B(0.5) C51B(0.5) H51B(0.5) C50B(0.5) H50B(0.5) C49B(0.5)
 H49B(0.5) C48B(0.5) H48B(0.5) C55B(0.5) C54B(0.5) H54B(0.5) C53B(0.5)
 C52B(0.5) C57B(0.5) H57B(0.5) C56B(0.5) H56B(0.5) C58B(0.5) H58D(0.5)
 H58E(0.5) H58F(0.5) C59B(0.5) C60B(0.5) H60D(0.5) H60E(0.5) H60F(0.5)
 C64B(0.5) C63B(0.5) H63B(0.5) C62B(0.5) H62B(0.5) C61B(0.5) C66B(0.5)
 H66B(0.5) C65B(0.5) C72B(0.5) C71B(0.5) H71B(0.5) C70B(0.5) C69B(0.5)
 H69B(0.5) C68B(0.5) H68B(0.5) C67B(0.5) C73B(0.5) H73D(0.5) H73E(0.5)
 H73F(0.5) C74B(0.5) C75B(0.5) H75D(0.5) H75E(0.5) H75F(0.5) C76B(0.5)
 C81B(0.5) H81B(0.5) C80B(0.5) C79B(0.5) C78B(0.5) H78B(0.5) C77B(0.5)
 H77B(0.5) C82B(0.5) C87B(0.5) H87B(0.5) C86B(0.5) H86B(0.5) C85B(0.5)
 H85B(0.5) C84B(0.5) H84B(0.5) C83B(0.5) C88B(0.5) H88D(0.5) H88E(0.5)
 H88F(0.5) C89B(0.5) C90B(0.5) H90D(0.5) H90E(0.5) H90F(0.5)
7.a Me refined with riding coordinates:
 C90B(H90D,H90E,H90F)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C17(H17),
 C20(H20), C21(H21), C24(H24), C26(H26), C27(H27), C32(H32), C35(H35), C36(H36),
  C39(H39), C40(H40), C41(H41), C42(H42), C51A(H51A), C50A(H50A), C49A(H49A),
 C48A(H48A), C57A(H57A), C54A(H54A), C55A(H55A), C65A(H65A), C66A(H66A),
 C62A(H62A), C69A(H69A), C71A(H71A), C72A(H72A), C81A(H81A), C80A(H80A),
 C77A(H77A), C86A(H86A), C85A(H85A), C84A(H84A), C83A(H83A), C51B(H51B),
 C50B(H50B), C49B(H49B), C48B(H48B), C54B(H54B), C57B(H57B), C56B(H56B),
 C63B(H63B), C62B(H62B), C66B(H66B), C71B(H71B), C69B(H69B), C68B(H68B),
 C81B(H81B), C78B(H78B), C77B(H77B), C87B(H87B), C86B(H86B), C85B(H85B),
 C84B(H84B)
7.c Fitted hexagon refined as free rotating group:
 C37(C38,C39,C40,C41,C42), C47A(C46A,C51A,C50A,C49A,C48A), C56A(C57A,C52A,C53A,
 C54A,C55A), C63A(C64A,C65A,C66A,C61A,C62A), C68A(C69A,C70A,C71A,C72A,C67A),
 C76A(C81A,C80A,C79A,C78A,C77A), C87A(C86A,C85A,C84A,C83A,C82A), C47B(C46B,C51B,
 C50B,C49B,C48B), C55B(C54B,C53B,C52B,C57B,C56B), C64B(C63B,C62B,C61B,C66B,
 C65B), C72B(C71B,C70B,C69B,C68B,C67B), C76B(C81B,C80B,C79B,C78B,C77B),
 C82B(C87B,C86B,C85B,C84B,C83B)
7.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C58A(H58A,H58B,H58C),
 C60A(H60A,H60B,H60C), C73A(H73A,H73B,H73C), C75A(H75A,H75B,H75C), C88A(H88A,
 H88B,H88C), C90A(H90A,H90B,H90C), C58B(H58D,H58E,H58F), C60B(H60D,H60E,H60F),
 C73B(H73D,H73E,H73F), C75B(H75D,H75E,H75F), C88B(H88D,H88E,H88F)
;
_shelx_res_checksum              62557
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.538
_oxdiff_exptl_absorpt_empirical_full_min 0.727