Rational design of efficient photosensitizers based on cyclometalated iridium(III) complexes with 2-arylbenzimidazole and aromatic 1,3-diketone ligands
Tatarin, Sergei V.; Meshcheriakova, Elizaveta A.; Kozyukhin, Sergey; Emets, Victor; Bezzubov, Stanislav; Dalton Transactions  (2023) –; doi:10.1039/D3DT02789A

data_7714136
_publ_section_title
;
 Rational design of efficient photosensitizers based on cyclometalated
 iridium(III) complexes with 2-arylbenzimidazole and aromatic 1,3-diketone
 ligands
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02789A
_journal_year                    2023
_chemical_formula_moiety         '2(C29.5 H22.5 Ir0.5 N2 O4)'
_chemical_formula_sum            'C59 H45 Ir N4 O8'
_chemical_formula_weight         1130.19
_space_group_crystal_system      orthorhombic
_space_group_IT_number           30
_space_group_name_Hall           'P 2 -2bc'
_space_group_name_H-M_alt        'P n c 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-08-27 deposited with the CCDC.	2023-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.2455(14)
_cell_length_b                   13.7868(7)
_cell_length_c                   12.7980(6)
_cell_measurement_reflns_used    9713
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      30.25
_cell_measurement_theta_min      2.28
_cell_volume                     5160.2(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            82138
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.048
_diffrn_reflns_theta_max         25.048
_diffrn_reflns_theta_min         1.633
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_type              'fine-focus sealed X-ray tube'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.647
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6074
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1216 before and 0.0646 after correction.
The Ratio of minimum to maximum transmission is 0.8141.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_description       plate
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.690
_refine_diff_density_min         -0.822
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.40(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     643
_refine_ls_number_reflns         9157
_refine_ls_number_restraints     200
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0308
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0345P)^2^+12.8026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0747
_refine_ls_wR_factor_ref         0.0881
_reflns_Friedel_coverage         0.903
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                6649
_reflns_number_total             9157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02789a2.cif
_cod_data_source_block           mo_me2_200k_0m
_cod_database_code               7714136
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.857
_shelx_estimated_absorpt_t_min   0.581
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60(3)
 0.40(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N2-C9 \\sim N2-C36
 with sigma of 0.02
 N4-C37 \\sim N4-C41
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C36 \\sim C35 \\sim
C34 \\sim C38 \\sim C39 \\sim C40: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C30) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O3) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C024) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C41) = Uanis(C31) = Uanis(C33) = Uanis(C43) = Uanis(C32) = Uanis(C1A) =
Uanis(C42) = Uanis(C37) = Uanis(C1C) = Uanis(C1E) = Uanis(C1B) = Uanis(C1D)
5. Others
 Fixed Sof: C9(0.6) C10(0.6) H10(0.6) C11(0.6) H11(0.6) C12(0.6) H12(0.6)
 C13(0.6) H13(0.6) C14(0.6) H14(0.6) C41(0.5) C31(0.5) H31(0.5) C33(0.5)
 H33(0.5) C43(0.5) H43(0.5) C32(0.5) H32(0.5) C1A(0.5) H1A(0.5) C42(0.5)
 H42(0.5) C37(0.5) C1C(0.5) H1C(0.5) C1E(0.5) H1E(0.5) C1B(0.5) H1B(0.5)
 C1D(0.5) H1D(0.5) C36(0.4) C35(0.4) H35(0.4) C34(0.4) H34(0.4) C38(0.4)
 H38(0.4) C39(0.4) H39(0.4) C40(0.4) H40(0.4)
 Fixed U11: C01M(0.03274)
 Fixed U12: C01M(-0.00436)
 Fixed U13: C01M(0.00061)
 Fixed U22: C01M(0.0413)
 Fixed U23: C01M(-0.00306)
 Fixed U33: C01M(0.04499)
 Fixed X: Ir2(0)
 Fixed Y: Ir2(0.5)
 Fixed Z: Ir2(0.43135)
6.a Aromatic/amide H refined with riding coordinates:
 C006(H006), C6(H6), C18(H18), C16(H16), C28(H28), C3(H3), C00M(H00M),
 C24(H24), C17(H17), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C31(H31),
  C33(H33), C43(H43), C32(H32), C1A(H1A), C00W(H00W), C19(H19), C25(H25),
 C016(H016), C26(H26), C42(H42), C1C(H1C), C1E(H1E), C1B(H1B), C1D(H1D),
 C01B(H01B), C01C(H01C), C01O(H01O), C01R(H01R), C01T(H01T), C01U(H01U),
 C01X(H01X), C2(H2), C01Z(H01Z), C22(H22), C35(H35), C34(H34), C38(H38),
 C39(H39), C40(H40)
6.b Fitted hexagon refined as free rotating group:
 C9(C10,C11,C12,C13,C14), C41(C31,C33,C43,C32,C1A), C42(C37,C1C,C1E,C1B,C1D),
 C36(C35,C34,C38,C39,C40)
6.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C30(H30A,H30B,H30C), C021(H02A,H02B,H02C), C024(H02D,H02E,
 H02F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              11209
_shelx_fab_checksum              88558
_olex2_submission_special_instructions 'No special instructions were received'