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_7714145
_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         'C52.5 H36.5 Ag F1.5 Ir N6 O7.5 S0.5'
_chemical_formula_sum            'C52.5 H36.5 Ag F1.5 Ir N6 O7.5 S0.5'
_chemical_formula_weight         1215.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_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                 98.4680(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.8139(5)
_cell_length_b                   38.9724(16)
_cell_length_c                   21.0645(9)
_cell_measurement_reflns_used    9723
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      23.33
_cell_measurement_theta_min      2.24
_cell_volume                     10404.7(7)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       \w-scan
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1630
_diffrn_reflns_av_unetI/netI     0.0741
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       46
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            261403
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.050
_diffrn_reflns_theta_max         25.050
_diffrn_reflns_theta_min         1.690
_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    3.013
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6593
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0951 before and 0.0719 after correction.
The Ratio of minimum to maximum transmission is 0.8847.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       plate
_exptl_crystal_F_000             4792
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.574
_refine_diff_density_min         -1.530
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1187
_refine_ls_number_reflns         18417
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.1049
_refine_ls_R_factor_gt           0.0569
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0670P)^2^+27.5518P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1281
_refine_ls_wR_factor_ref         0.1475
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11542
_reflns_number_total             18417
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02789a2.cif
_cod_data_source_block           mo_me4_neo_0m
_cod_original_formula_sum        'C52.50 H36.50 Ag F1.50 Ir N6 O7.50 S0.50'
_cod_database_code               7714145
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.773
_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, All O(H) groups
2. Restrained distances
 Ag3-Ag4
 2.9 with sigma of 0.01
 N8-C10 \\sim N8-C15
 with sigma of 0.02
 N4-C5 \\sim N4-C0
 with sigma of 0.02
 O12-C02N \\sim O0-C02N
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C1G) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C0) = Uanis(C29) = Uanis(C27) = Uanis(C30) = Uanis(C9B) = Uanis(C28) =
Uanis(C5) = Uanis(C8) = Uanis(C6) = Uanis(C9) = Uanis(C9A) = Uanis(C7)
Uanis(C10) = Uanis(C11) = Uanis(C14) = Uanis(C12) = Uanis(C31B) = Uanis(C13) =
Uanis(C15) = Uanis(C16) = Uanis(C19) = Uanis(C17) = Uanis(C31A) = Uanis(C18)
Uanis(C20) = Uanis(C21) = Uanis(C25) = Uanis(C24) = Uanis(C23) = Uanis(C22) =
Uanis(C1A) = Uanis(C1B) = Uanis(C1F) = Uanis(C1E) = Uanis(C1D) = Uanis(C1C)
4. Others
 Fixed Sof: Ag1(0.9) Ag2(0.9) H10(0.5) H3(0.5) O0(0.7) C20(0.4) C21(0.4)
 H21(0.4) C25(0.4) H25(0.4) C24(0.4) H24(0.4) C23(0.4) H23(0.4) C22(0.4)
 H22(0.4) C10(0.33333) C11(0.33333) H11(0.33333) C14(0.33333) H14(0.33333)
 C12(0.33333) H12(0.33333) C31B(0.33333) H31B(0.33333) C13(0.33333)
 H13(0.33333) C0(0.7) C29(0.7) H29(0.7) C27(0.7) H27(0.7) C30(0.7) H30(0.7)
 C9B(0.7) H9B(0.7) C28(0.7) H28(0.7) C26(0.7) H26A(0.7) H26B(0.7) H26C(0.7)
 C5(0.3) C8(0.3) H8(0.3) C6(0.3) H6(0.3) C9(0.3) H9(0.3) C9A(0.3) H9A(0.3)
 C7(0.3) H7(0.3) C15(0.66667) C16(0.66667) H16(0.66667) C19(0.66667)
 H19(0.66667) C17(0.66667) H17(0.66667) C31A(0.66667) H31A(0.66667)
 C18(0.66667) H18(0.66667) Ag4(0.1) Ag3(0.1) C1A(0.6) C1B(0.6) H1B(0.6)
 C1F(0.6) H1F(0.6) C1E(0.6) H1E(0.6) C1D(0.6) H1D(0.6) C1C(0.6) H1C(0.6)
 O12(0.3) C1G(0.3) H1GA(0.3) H1GB(0.3) H1GC(0.3)
5.a Rotating group with stretchable bonds:
 O10(H10)
5.b Aromatic/amide H refined with riding coordinates:
 C00X(H00X), C014(H014), C017(H017), C01B(H01B), C01E(H01E), C01I(H01I),
 C01N(H01N), C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S), C01T(H01T),
 C01U(H01U), C01W(H01W), C022(H022), C025(H025), C026(H026), C027(H027),
 C02A(H02A), C02B(H02B), C02C(H02C), C02F(H02F), C02H(H02H), C21(H21), C25(H25),
  C24(H24), C23(H23), C22(H22), C02L(H02L), C11(H11), C14(H14), C12(H12),
 C31B(H31B), C13(H13), C02R(H02R), C02S(H02S), C02U(H02U), C02V(H02V), C29(H29),
  C27(H27), C30(H30), C9B(H9B), C28(H28), C02X(H02X), C02Y(H02Y), C02Z(H02Z),
 C030(H030), C032(H032), C034(H034), C036(H036), C037(H037), C039(H039),
 C03B(H03D), C03E(H03E), C03G(H03G), C03H(H03H), C03I(H03I), C03M(H03M),
 C03Z(H03Z), C040(H040), C8(H8), C6(H6), C9(H9), C9A(H9A), C7(H7), C16(H16),
 C19(H19), C17(H17), C31A(H31A), C18(H18), C1B(H1B), C1F(H1F), C1E(H1E),
 C1D(H1D), C1C(H1C)
5.c Fitted hexagon refined as free rotating group:
 C20(C21,C25,C24,C23,C22), C10(C11,C14,C12,C31B,C13), C0(C29,C27,C30,C9B,C28),
 C5(C8,C6,C9,C9A,C7), C15(C16,C19,C17,C31A,C18), C1A(C1B,C1F,C1E,C1D,C1C)
5.d Idealised Me refined as rotating group:
 C02P(H02D,H02E,H02G), C031(H03A,H03B,H03C), C26(H26A,H26B,H26C), C03S(H03F,
 H03J,H03K), C1G(H1GA,H1GB,H1GC)
5.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              63768
_shelx_fab_checksum              89316
_olex2_submission_special_instructions 'No special instructions were received'