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_7248233
_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         'C60 H63 Ir N5 O5, B F4, 0.5(C4 H10 O)'
_chemical_formula_sum            'C62 H68 B F4 Ir N5 O5.5'
_chemical_formula_weight         1250.22
_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
_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                100.368(2)
_cell_angle_beta                 91.400(2)
_cell_angle_gamma                104.629(2)
_cell_formula_units_Z            2
_cell_length_a                   9.7337(2)
_cell_length_b                   16.3240(3)
_cell_length_c                   18.6845(4)
_cell_measurement_reflns_used    36776
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.9930
_cell_measurement_theta_min      2.7690
_cell_volume                     2818.06(10)
_computing_cell_refinement
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)
;
_computing_data_collection
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)
;
_computing_data_reduction
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)
;
_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 0.994
_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    -31.00  77.00   1.00   16.00    --  -13.00  72.00 150.00  108
  2  \w    -67.00  23.00   1.00   16.00    --  -13.00 -72.00  30.00   90
  3  \w    -70.00  23.00   1.00   16.00    --  -13.00 -72.00-150.00   93
  4  \w    -83.00 -17.00   1.00   16.00    --  -13.00   0.00  30.00   66
  5  \w    -31.00  77.00   1.00   16.00    --  -13.00  72.00-150.00  108
  6  \w    -69.00  23.00   1.00   16.00    --  -13.00 -72.00  90.00   92
  7  \w    -63.00 -23.00   1.00   16.00    --  -13.00 -72.00 -90.00   40
  8  \w    -83.00  -8.00   1.00   16.00    --  -13.00   0.00  90.00   75
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_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      -0.0238821000
_diffrn_orient_matrix_UB_12      -0.0258809000
_diffrn_orient_matrix_UB_13      -0.0349718000
_diffrn_orient_matrix_UB_21      -0.0195562000
_diffrn_orient_matrix_UB_22      -0.0371910000
_diffrn_orient_matrix_UB_23      0.0159473000
_diffrn_orient_matrix_UB_31      -0.0689187000
_diffrn_orient_matrix_UB_32      0.0064196000
_diffrn_orient_matrix_UB_33      0.0044801000
_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  0.0285
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            48362
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         2.363
_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    2.437
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85139
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.473
_exptl_crystal_description       block
_exptl_crystal_F_000             1274
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.933
_refine_diff_density_min         -1.015
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     994
_refine_ls_number_reflns         12877
_refine_ls_number_restraints     603
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0310
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0427P)^2^+3.3739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0758
_refine_ls_wR_factor_ref         0.0781
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11538
_reflns_number_total             12877
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ra06764e2.cif
_cod_data_source_block           IrepqcL3
_cod_original_formula_sum        'C62 H68 B F4 Ir N5 O5.50'
_cod_database_code               7248233
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ir C60 H63 N5 O5 B F4'
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.727
_reflns_odcompleteness_completeness 99.41
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29-C36 \\sim C29-C36B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O71B \\sim C72B \\sim C73B \\sim C71B \\sim C74B \\sim O71 \\sim C72 \\sim C73
\\sim C71 \\sim C74: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
4. Rigid body (RIGU) restrains
 O1, O2, N1, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15,
 C16, C17, C18, O21, O22, C36, C37, C38, O1B, O2B, N1B, C1B, C2B, C3B, C4B, C5B,
  C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B, C14B, C15B, C16B, C17B, C18B,
 O21B, O22B, C36B, C37B, C38B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O71B, C72B, C73B, C71B, C74B, O71, C72, C73, C71, C74
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{O1, O2, N1, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15,
C16, C17, C18} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1B, O2B, N1B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B,
C13B, C14B, C15B, C16B, C17B, C18B}
{O21, O22, C36, C37, C38} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O21B, O22B, C36B, C37B, C38B}
6. Others
 Sof(O1B)=Sof(O2B)=Sof(N1B)=Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=
 Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(C8B)=Sof(H8B)=
 Sof(C9B)=Sof(C10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=Sof(H13B)=
 Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(C16B)=Sof(C17B)=Sof(H17C)=Sof(H17D)=
 Sof(C18B)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(O1)=Sof(O2)=Sof(N1)=Sof(C1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=
 Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=
 Sof(C15)=Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=FVAR(1)
 Sof(O21B)=Sof(O22B)=Sof(C36B)=Sof(C37B)=Sof(H37C)=Sof(H37D)=Sof(C38B)=
 Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(2)
 Sof(O21)=Sof(O22)=Sof(C36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(H38C)=FVAR(2)
 Sof(O71B)=Sof(C71B)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72B)=Sof(H72C)=
 Sof(H72D)=Sof(C73B)=Sof(H73C)=Sof(H73D)=Sof(C74B)=Sof(H74D)=Sof(H74E)=
 Sof(H74F)=0.5*(1-FVAR(4))
 Sof(O71)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=0.5*FVAR(4)
7.a Free rotating group:
 O71(C71,H71A,H71B,H71C,C72,H72A,H72B,C73,H73A,H73B,C74,H74A,H74B,H74C,O71B,
 C71B,H71D,H71E,H71F,C72B,H72C,H72D,C73B,H73C,H73D,C74B,H74D,H74E,H74F)
7.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,
 H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B),
 C62(H62A,H62B), C63(H63A,H63B), C17(H17A,H17B), C37(H37A,H37B), C17B(H17C,
 H17D), C37B(H37C,H37D)
7.c Aromatic/amide H refined with riding coordinates:
 N43(H43), C41(H41), C42(H42), C44(H44), C47(H47), C49(H49), C50(H50), C2(H2),
 C3(H3), C4(H4), C5(H5), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14),
 C22(H22), C23(H23), C24(H24), C25(H25), C28(H28), C31(H31), C32(H32), C33(H33),
  C34(H34), C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B), C8B(H8B), C11B(H11B),
 C12B(H12B), C13B(H13B), C14B(H14B)
7.d Idealised Me refined as rotating group:
 C52(H52A,H52B,H52C), C64(H64A,H64B,H64C), C18(H18A,H18B,H18C), C38(H38A,H38B,
 H38C), C18B(H18D,H18E,H18F), C38B(H38D,H38E,H38F)
;
_shelx_res_checksum              33289
_olex2_submission_original_sample_id AG009
_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 3.354
_oxdiff_exptl_absorpt_empirical_full_min 0.434