Alkyl chain functionalised Ir(iii) complexes: synthesis, properties and behaviour as emissive dopants in microemulsions
Stokes, Emily C.; Shoetan, Ibrahim O.; Gillman, Alice M.; Horton, Peter N.; Coles, Simon J.; Woodbury, Simon E.; Fallis, Ian A.; Pope, Simon J. A.; RSC Advances 14 (2024) 6987–6997; doi:10.1039/D3RA06764E

data_7248232
_publ_section_title
;
 Alkyl chain functionalised Ir(iii) complexes: synthesis, properties and
 behaviour as emissive dopants in microemulsions
;
_journal_issue                   10
_journal_name_full               'RSC Advances'
_journal_page_first              6987
_journal_page_last               6997
_journal_paper_doi               10.1039/D3RA06764E
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'C40 H34 Ir N4 O4, C4 H10 O, B F4'
_chemical_formula_sum            'C44 H44 B F4 Ir N4 O5'
_chemical_formula_weight         987.84
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-19 deposited with the CCDC.	2024-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                119.195(2)
_cell_angle_beta                 91.698(2)
_cell_angle_gamma                102.782(2)
_cell_formula_units_Z            2
_cell_length_a                   8.7992(2)
_cell_length_b                   16.6146(4)
_cell_length_c                   16.7086(4)
_cell_measurement_reflns_used    31963
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.8680
_cell_measurement_theta_min      2.6270
_cell_volume                     2052.24(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_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      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -63.00  73.00   1.00   45.00    --  -17.00  18.00 -30.00  136
  2  \w    -78.00  12.00   1.00   45.00    --  -17.00 -72.00 150.00   90
  3  \w    -31.00  39.00   1.00   45.00    --  -17.00  54.00  30.00   70
  4  \w    -53.00  22.00   1.00   45.00    --  -17.00 -72.00 -60.00   75
  5  \w    -32.00  18.00   1.00   45.00    --  -17.00  72.00  60.00   50
  6  \w   -107.00  73.00   1.00   45.00    --  -17.00   0.00 -30.00  180
  7  \w    -75.00  22.00   1.00   45.00    --  -17.00 -72.00 120.00   97
  8  \w    -78.00  22.00   1.00   45.00    --  -17.00 -72.00 -30.00  100
  9  \w    -35.00  49.00   1.00   45.00    --  -17.00  72.00 150.00   84
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with VHF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0666866000
_diffrn_orient_matrix_UB_12      -0.0334720000
_diffrn_orient_matrix_UB_13      -0.0006435000
_diffrn_orient_matrix_UB_21      0.0452754000
_diffrn_orient_matrix_UB_22      -0.0048629000
_diffrn_orient_matrix_UB_23      0.0324351000
_diffrn_orient_matrix_UB_31      -0.0227700000
_diffrn_orient_matrix_UB_32      0.0378920000
_diffrn_orient_matrix_UB_33      0.0370905000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            40539
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.405
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    3.322
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.599
_exptl_crystal_description       needle
_exptl_crystal_F_000             988
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.820
_refine_diff_density_min         -1.049
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         9389
_refine_ls_number_restraints     415
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0264
_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^)+(0.0470P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0658
_refine_ls_wR_factor_ref         0.0674
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8509
_reflns_number_total             9389
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ra06764e2.cif
_cod_data_source_block           cisIrepqc
_cod_original_cell_volume        2052.24(9)
_cod_database_code               7248232
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C40 H34 Ir N4 O4 B F4'
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.619
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1B-F2B \\sim F1B-F3B \\sim F1B-F4B \\sim F2B-F3B \\sim F2B-F4B \\sim F3B-F4B
 with sigma of 0.04
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4
 with sigma of 0.04
 B1B-F1B \\sim B1B-F2B \\sim B1B-F3B \\sim B1B-F4B
 with sigma of 0.02
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
B1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim B1B \\sim F1B \\sim F2B \\sim F3B
\\sim F4B \\sim C64 \\sim O61 \\sim C61 \\sim C63 \\sim C62 \\sim O61B \\sim
C61B \\sim C63B \\sim C62B \\sim C64B: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 B1B, F1B, F2B, F3B, F4B, F1, B1, F2, F3, F4, C64B, O61B, C61B, C63B, C62B,
 C63, O61, C61, C62, C64
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{O61, C61, C62, C63, C64} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O61B, C61B, C62B, C63B, C64B}
6. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(B1B)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(1)
 Sof(O61B)=Sof(C61B)=Sof(H61C)=Sof(H61D)=Sof(C62B)=Sof(H62D)=Sof(H62E)=
 Sof(H62F)=Sof(C63B)=Sof(H63C)=Sof(H63D)=Sof(C64B)=Sof(H64D)=Sof(H64E)=
 Sof(H64F)=1-FVAR(2)
 Sof(O61)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C37(H37A,H37B), C61(H61A,H61B), C63(H63A,H63B), C61B(H61C,
 H61D), C63B(H63C,H63D)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C22(H22), C23(H23), C24(H24), C25(H25), C28(H28), C32(H32), C33(H33),
  C34(H34), C35(H35)
7.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C38(H38A,H38B,H38C), C42(H42A,H42B,H42C), C52(H52A,H52B,
 H52C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C62B(H62D,H62E,H62F),
 C64B(H64D,H64E,H64F)
;
_shelx_res_checksum              66908
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_original_sample_id AG006
_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 3.833
_oxdiff_exptl_absorpt_empirical_full_min 0.379