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_7714146
_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
'0.667(C54 H33.5 Ir N6 O4 S2), 0.333(C F3 O3 S), 2.25(C2 H3 N)'
_chemical_formula_sum            'C40.83 H29.08 F Ir0.67 N6.25 O3.67 S1.67'
_chemical_formula_weight         866.52
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                80.1990(10)
_cell_angle_beta                 71.5230(10)
_cell_angle_gamma                81.6440(10)
_cell_formula_units_Z            12
_cell_length_a                   20.2850(8)
_cell_length_b                   21.1480(8)
_cell_length_c                   28.2673(11)
_cell_measurement_reflns_used    9795
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      30.40
_cell_measurement_theta_min      2.29
_cell_volume                     11279.1(8)
_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
_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  0.0472
_diffrn_reflns_av_unetI/netI     0.0565
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            163620
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.999
_diffrn_reflns_theta_min         1.338
_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    2.525
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5502
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0850 before and 0.0503 after correction.
The Ratio of minimum to maximum transmission is 0.8493.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_description       block
_exptl_crystal_F_000             5210
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.971
_refine_diff_density_min         -0.744
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2900
_refine_ls_number_reflns         54411
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0558
_refine_ls_R_factor_gt           0.0373
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0257P)^2^+10.7718P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0723
_refine_ls_wR_factor_ref         0.0780
_reflns_Friedel_coverage         0.000
_reflns_number_gt                42917
_reflns_number_total             54411
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02789a2.cif
_cod_data_source_block           me9
_cod_database_code               7714146
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.786
_shelx_estimated_absorpt_t_min   0.673
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H08X,H08Y,H} of C08U
 At 1.5 times of:
  All O(H) groups, {H20D,H20E,H20F} of C20A, {H20A,H20B,H20C} of C20B, {H9AA,
  H9AB,H9AC} of C9A, {H06N,H06Q,H06S} of C06Q, {H08N,H08P,H08Q} of C08N, {H08U,
  H08V,H08W} of C08Y, {H08F,H08H,H08I} of C08F, {H21A,H21B,H21C} of C21, {H08R,
  H08S,H08T} of C08Q, {H08J,H08K,H08M} of C08D, {H9A,H9B,H9C} of C9, {H08A,H08B,
  H08D} of C08H, {H07I,H07L,H07M} of C07D, {H07P,H07Q,H07S} of C07L, {H07D,H07F,
  H07H} of C07Q
2. Restrained distances
 N01A-C0 \\sim N01A-C6
 with sigma of 0.02
 N02G-C13 \\sim N02G-C19
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O01P) \\sim Ueq, Uanis(O02J) \\sim Ueq: with sigma of 0.0025 and sigma
for terminal atoms of 0.005
Uanis(C08N) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C22) \\sim Ueq, Uanis(N23) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F04Y) \\sim Ueq, Uanis(C08U) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(N0) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C08Y) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) = Uanis(C15) = Uanis(C17) = Uanis(C16) = Uanis(C18) = Uanis(C14) =
Uanis(C19) = Uanis(C1B) = Uanis(C1D) = Uanis(C1C) = Uanis(C1E) = Uanis(C1A)
Uanis(C2) = Uanis(C0) = Uanis(C1) = Uanis(C4) = Uanis(C3) = Uanis(C24) =
Uanis(C8) = Uanis(C6) = Uanis(C7) = Uanis(C11) = Uanis(C10) = Uanis(C12)
4. Others
 Fixed Sof: H00G(0.5) H00J(0.5) H01P(0.5) H01S(0.5) C13(0.5) C15(0.5) H15(0.5)
 C17(0.5) H17(0.5) C16(0.5) H16(0.5) C18(0.5) H18(0.5) C14(0.5) H14(0.5)
 N0(0.55) C2(0.5) H2(0.5) C0(0.5) C1(0.5) H1(0.5) C4(0.5) H4(0.5) C3(0.5)
 H3(0.5) C24(0.5) H24(0.5) C9(0.8) H9A(0.8) H9B(0.8) H9C(0.8) C21(0.7)
 H21A(0.7) H21B(0.7) H21C(0.7) C20(0.7) N2(0.7) C08U(0.8) H08X(0.8) H08Y(0.8)
 H(0.8) C8(0.5) H8(0.5) C6(0.5) C7(0.5) H7(0.5) C11(0.5) H11(0.5) C10(0.5)
 H10(0.5) C12(0.5) H12(0.5) C19(0.5) C1B(0.5) H1B(0.5) C1D(0.5) H1D(0.5)
 C1C(0.5) H1C(0.5) C1E(0.5) H1E(0.5) C1A(0.5) H1A(0.5) C21B(0.55) C22(0.8)
 N23(0.8) C20B(0.55) H20A(0.55) H20B(0.55) H20C(0.55) C20A(0.45) H20D(0.45)
 H20E(0.45) H20F(0.45) C21A(0.45) N3(0.45) C9A(0.2) H9AA(0.2) H9AB(0.2)
 H9AC(0.2)
5.a Riding coordinates:
 O00G(H00G), O00J(H00J), O01P(H01P), O01S(H01S), C07Q(H07D,H07F,H07H),
 C08U(H08X,H08Y,H), C20B(H20A,H20B,H20C)
5.b Aromatic/amide H refined with riding coordinates:
 C01Z(H01Z), C02C(H02C), C02D(H02D), C02E(H02E), C02K(H02K), C02M(H02M),
 C02Q(H02Q), C02U(H02U), C02X(H02X), C02Y(H02Y), C031(H031), C032(H032),
 C036(H036), C037(H037), C03A(H03A), C03F(H03F), C03G(H03G), C03I(H03I),
 C03K(H03K), C03O(H03O), C03P(H03P), C03Q(H03Q), C03T(H03T), C03V(H03V),
 C03X(H03X), C03Y(H03Y), C040(H040), C041(H041), C042(H042), C044(H044),
 C048(H048), C04D(H04D), C04I(H04I), C04J(H04J), C04N(H04N), C04O(H04O),
 C04P(H04P), C04Q(H04Q), C04U(H04U), C04V(H04V), C04W(H04W), C04X(H04X),
 C050(H050), C051(H051), C053(H053), C054(H054), C055(H055), C057(H057),
 C059(H059), C05A(H05A), C05B(H05B), C05D(H05D), C05E(H05E), C05H(H05H),
 C05K(H05K), C05M(H05M), C05N(H05N), C15(H15), C17(H17), C16(H16), C18(H18),
 C14(H14), C05S(H05S), C05T(H05T), C05W(H05W), C05X(H05X), C05Y(H05Y),
 C05Z(H05Z), C063(H063), C064(H064), C066(H066), C067(H067), C068(H068),
 C069(H069), C06A(H06A), C06B(H06B), C06C(H06C), C06D(H06D), C06E(H06E),
 C06F(H06F), C06G(H06G), C06H(H06H), C06I(H06I), C06J(H06J), C06K(H06K),
 C06L(H06L), C06M(H06M), C06O(H06O), C06P(H06P), C06R(H06R), C06T(H06T),
 C06U(H06U), C06V(H06V), C06X(H06X), C06Y(H06Y), C06Z(H06Z), C070(H070),
 C071(H071), C073(H073), C074(H074), C075(H075), C078(H078), C07A(H07A),
 C07B(H07B), C07C(H07C), C07E(H07E), C07G(H07G), C07J(H07J), C07K(H07K), C2(H2),
  C1(H1), C4(H4), C3(H3), C24(H24), C07N(H07N), C07O(H07O), C07R(H07R),
 C07X(H07X), C07Z(H07Z), C080(H080), C081(H081), C082(H082), C084(H084),
 C08C(H08C), C08E(H08E), C08G(H08G), C08L(H08L), C08O(H08O), C8(H8), C7(H7),
 C11(H11), C10(H10), C12(H12), C1B(H1B), C1D(H1D), C1C(H1C), C1E(H1E), C1A(H1A)
5.c Fitted hexagon refined as free rotating group:
 C13(C15,C17,C16,C18,C14), C2(C0,C1,C4,C3,C24), C8(C6,C7,C11,C10,C12), C19(C1B,
 C1D,C1C,C1E,C1A)
5.d Idealised Me refined as rotating group:
 C06Q(H06N,H06Q,H06S), C07D(H07I,H07L,H07M), C07L(H07P,H07Q,H07S), C9(H9A,H9B,
 H9C), C08D(H08J,H08K,H08M), C08F(H08F,H08H,H08I), C08H(H08A,H08B,H08D),
 C21(H21A,H21B,H21C), C08N(H08N,H08P,H08Q), C08Q(H08R,H08S,H08T), C08Y(H08U,
 H08V,H08W), C20A(H20D,H20E,H20F), C9A(H9AA,H9AB,H9AC)
5.e Idealised tetrahedral OH refined as rotating group:
 O00K(H00K), O00O(H00O), O015(H015), O017(H017)
;
_shelx_res_checksum              76457
_olex2_submission_special_instructions 'No special instructions were received'