Methylated regioisomers of Re(I) and Ir(III) tetrazole complexes: photophysical properties and optical imaging of brain tissue
Dallerba, Elena; Cameron, Lee; Armstrong, Blake I.; Ellison, Gaewyn; Turner, Eva; Innes, Evelyn; Strickling, Georgia L.; Pangiarella, Joel Ethan; O'Conghaile, Peter; Nesbit, Michael; Moggach, Stephen A.; Raiteri, Paolo; Stagni, Stefano; Pearson, Emma; Hackett, Mark; Massi, Massimiliano; Dalton Transactions  (2025) –; doi:10.1039/D5DT01745A

data_7719883
_publ_section_title
;
 Methylated regioisomers of Re(I) and Ir(III) tetrazole complexes:
 photophysical properties and optical imaging of brain tissue
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT01745A
_journal_year                    2025
_chemical_formula_moiety         'C29 H23 Ir N7, C3 H6 O, F6 P'
_chemical_formula_sum            'C32 H29 F6 Ir N7 O P'
_chemical_formula_weight         864.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2dlrc4
_audit_creation_date             2022-10-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-28 deposited with the CCDC.	2025-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.4208(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.95004(6)
_cell_length_b                   13.30076(5)
_cell_length_c                   17.34384(7)
_cell_measurement_reflns_used    57718
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.2050
_cell_measurement_theta_min      4.2830
_cell_volume                     3210.54(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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     34.00 119.00   0.50    0.05    --   46.32  41.00 -25.00  170
  2  \w     32.00 118.00   0.50    0.05    --   46.32  57.00  60.00  172
  3  \w     32.00 118.00   0.50    0.05    --   46.32  57.00  90.00  172
  4  \w     34.00 119.00   0.50    0.05    --   46.32  38.00 150.00  170
  5  \w    -46.00  26.00   0.50    0.05    --  -46.32  41.00 -25.00  144
  6  \w    -69.00  26.00   0.50    0.05    --  -46.32  77.00 -90.00  190
  7  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00-180.00   82
  8  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00   0.00   82
  9  \w   -105.00 -30.00   0.50    0.05    -- -102.29  77.00  30.00  150
 10  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00  90.00   82
 11  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00 120.00   82
 12  \w    -71.00 -30.00   0.50    0.05    -- -102.29  61.00 150.00   82
 13  \w   -119.00 -33.00   0.50    0.05    --  -46.32 -38.00 150.00  172
 14  \w   -174.00 -80.00   0.50    0.05    -- -102.29 -77.00 120.00  188
 15  \w   -174.00 -80.00   0.50    0.05    -- -102.29 -77.00  90.00  188
 16  \w   -174.00 -79.00   0.50    0.05    -- -102.29 -78.00  72.54  190
 17  \w   -174.00 -80.00   0.50    0.05    -- -102.29 -77.00  60.00  188
 18  \w   -174.00 -81.00   0.50    0.05    -- -102.29 -73.00 102.98  186
 19  \w   -174.00 -80.00   0.50    0.05    -- -102.29 -77.00 138.93  188
 20  \w   -174.00 -83.00   0.50    0.05    -- -102.29 -69.00 123.87  182
 21  \w   -174.00 -83.00   0.50    0.05    -- -102.29 -69.00  91.90  182
 22  \w   -174.00 -83.00   0.50    0.05    -- -102.29 -69.00  44.60  182
 23  \w   -174.00 -83.00   0.50    0.05    -- -102.29 -68.00  75.75  182
 24  \w   -174.00 -85.00   0.50    0.05    -- -102.29 -64.00  94.28  178
 25  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -62.00 123.64  176
 26  \w   -174.00 -84.00   0.50    0.05    -- -102.29 -65.00 148.26  180
 27  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00  60.00  176
 28  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -61.00  46.08  176
 29  \w   -174.00 -86.00   0.50    0.05    -- -102.29 -60.00  62.26  176
 30  \w   -174.00 -88.00   0.50    0.05    -- -102.29 -54.00  86.47  172
 31  \w   -174.00 -88.00   0.50    0.05    -- -102.29 -53.00 117.64  172
 32  \w   -174.00 -88.00   0.50    0.05    -- -102.29 -53.00  67.24  172
 33  \w   -174.00 -88.00   0.50    0.05    -- -102.29 -48.00  67.56  172
 34  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00  60.00  168
 35  \w   -174.00 -89.00   0.50    0.05    -- -102.29 -51.00  11.05  170
 36  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00  30.00  168
 37  \w   -174.00 -88.00   0.50    0.05    -- -102.29 -48.00 -99.61  172
 38  \w   -175.00 -90.00   0.50    0.05    -- -102.29 -41.00-178.00  170
 39  \w   -119.00 -34.00   0.50    0.05    --  -46.32 -41.00-178.00  170
 40  \w   -108.00 -30.00   0.50    0.05    -- -102.29 108.00 -60.75  156
 41  \w   -174.00 -90.00   0.50    0.05    -- -102.29 -45.00  90.00  168
 42  \w   -174.00 -79.00   0.50    0.05    -- -102.29 -82.00 129.39  190
 43  \w   -118.00 -73.00   0.50    0.05    --  -46.32-125.00   0.00   90
 44  \w   -118.00 -73.00   0.50    0.05    --  -46.32-125.00 -90.00   90
 45  \w     33.00  69.00   0.50    0.05    --  102.29 -61.00-180.00   72
 46  \w     30.00 101.00   0.50    0.05    --  102.29-125.00  90.00  142
 47  \w     30.00  71.00   0.50    0.05    --  102.29 -61.00   0.00   82
 48  \w    -28.00  26.00   0.50    0.05    --   46.32 -19.00  30.00  108
 49  \w    -26.00  46.00   0.50    0.05    --   46.32 -41.00-178.00  144
 50  \w    119.00 160.00   0.50    0.05    --  102.29 125.00-150.00   82
 51  \w     75.00 104.00   0.50    0.05    --  102.29 125.00-150.00   58
 52  \w    131.00 177.00   0.50    0.05    --  102.29  15.00-120.00   92
 53  \w    132.00 165.00   0.50    0.05    --  102.29  77.00  90.00   66
 54  \w     80.00 174.00   0.50    0.05    --  102.29  77.00  60.00  188
 55  \w     90.00 175.00   0.50    0.05    --  102.29  41.00 -25.00  170
 56  \w     80.00 106.00   0.50    0.05    --  102.29  77.00  90.00   52
 57  \w     89.00 131.00   0.50    0.05    --  102.29  61.00 120.00   84
 58  \w     86.00 112.00   0.50    0.05    --  102.29  61.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0555032000
_diffrn_orient_matrix_UB_12      0.0127343000
_diffrn_orient_matrix_UB_13      0.0936870000
_diffrn_orient_matrix_UB_21      0.0793465000
_diffrn_orient_matrix_UB_22      0.0582483000
_diffrn_orient_matrix_UB_23      -0.0179393000
_diffrn_orient_matrix_UB_31      -0.0536689000
_diffrn_orient_matrix_UB_32      0.0992959000
_diffrn_orient_matrix_UB_33      -0.0014902000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0163
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            94362
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.334
_diffrn_reflns_theta_min         3.175
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.180
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77869
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.789
_exptl_crystal_description       block
_exptl_crystal_F_000             1696
_exptl_crystal_recrystallization_method
'formed from the slow evaporation of acetone from an acetone and water solution.'
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.116
_exptl_crystal_size_min          0.097
_refine_diff_density_max         3.142
_refine_diff_density_min         -2.615
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         6566
_refine_ls_number_restraints     179
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0385
_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^)+(0.0595P)^2^+18.4436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6366
_reflns_number_total             6566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01745a2.cif
_cod_data_source_block           mxm543rm_auto
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7719883
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C29 H23 Ir1 N7 P1 F6'
_chemical_oxdiff_usercomment     'Lee Cameron'
_shelx_estimated_absorpt_t_max   0.470
_shelx_estimated_absorpt_t_min   0.329
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
2. Restrained distances
 F6A-F3A
 2.328 with sigma of 0.02
 F3A-F5A
 2.328 with sigma of 0.02
 F5A-F4A
 2.328 with sigma of 0.02
 F6A-F4A
 2.328 with sigma of 0.02
 P1-F6 \\sim P1-F1 \\sim P1-F5 \\sim P1-F2 \\sim P1-F3 \\sim P1-F4
 with sigma of 0.02
 F6-F1 \\sim F6-F2 \\sim F6-F3 \\sim F6-F4 \\sim F5-F1 \\sim F5-F2 \\sim F5-F3
\\sim F5-F4
 with sigma of 0.04
 F6-F5 \\sim F1-F2 \\sim F4-F3
 with sigma of 0.05
 P1-F5 \\sim P1-F5A \\sim P1-F3 \\sim P1-F3A \\sim P1-F6 \\sim P1-F6A \\sim
P1-F4 \\sim P1-F4A \\sim P1-F2 ~
 P1-F1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
P1 \\sim F6 \\sim F1 \\sim F5 \\sim F2 \\sim F3 \\sim F4: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F3) = Uanis(F5A) = Uanis(F3A) = Uanis(F4) = Uanis(F6A) = Uanis(F4A) =
Uanis(F6) = Uanis(F5)
4. Rigid body (RIGU) restrains
 P1, F6, F1, F5, F2, F3, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F6A)=Sof(F5A)=Sof(F3A)=Sof(F4A)=1-FVAR(1)
 Sof(F6)=Sof(F5)=Sof(F3)=Sof(F4)=FVAR(1)
6.a Free rotating group:
 P1(F6,F1,F5,F2,F3,F4)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C5(H5), C27(H27), C17(H17), C8(H8), C6(H6), C22(H22),
 C26(H26), C25(H25), C21(H21), C20(H20), C19(H19), C28(H28), C14(H14), C16(H16),
  C9(H9), C15(H15), C11(H11), C10(H10)
6.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              32375
_olex2_exptl_crystal_mounting_method
'mounted on a glass fibre using silicon oil'
_olex2_submission_original_sample_id 'mxm543rm - IrPTzN2'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.240
_oxdiff_exptl_absorpt_empirical_full_min 0.851