Unusually Fast Phosphorescence from Ir(III) Complexes via Dinuclear Molecular Design.
Shafikov, Marsel Z.; Daniels, Ruth; Kozhevnikov, Valery N.; The journal of physical chemistry letters  (2019) 7015–7024; doi:10.1021/acs.jpclett.9b03002

data_8000322
_publ_section_title
;
 Unusually Fast Phosphorescence from Ir(III) Complexes via Dinuclear
 Molecular Design.
;
_journal_name_full               'The journal of physical chemistry letters'
_journal_page_first              7015
_journal_page_last               7024
_journal_paper_doi               10.1021/acs.jpclett.9b03002
_journal_year                    2019
_chemical_formula_moiety         'C96 H84 Cl2 Ir2 N10, 3(C H4 O)'
_chemical_formula_sum            'C99 H96 Cl2 Ir2 N10 O3'
_chemical_formula_weight         1929.15
_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     direct
_audit_creation_date             2016-10-18
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.10.10 svn.r3347 for OlexSys, GUI svn.r5252)
;
_cell_angle_alpha                74.6940(10)
_cell_angle_beta                 79.2030(10)
_cell_angle_gamma                80.8400(10)
_cell_formula_units_Z            2
_cell_length_a                   14.7346(2)
_cell_length_b                   14.9699(3)
_cell_length_c                   23.4455(3)
_cell_measurement_reflns_used    49403
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      73.5500
_cell_measurement_theta_min      4.5520
_cell_volume                     4866.79(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.37b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.37b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.37b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1773
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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   -116.00 -18.00   1.00    2.00    --  -41.88 -37.00 150.00   98
  2  \w   -118.00  -9.00   1.00    2.00    --  -41.88 -77.00 -60.00  109
  3  \w    -66.00  33.00   1.00    2.00    --  -41.88  37.00 150.00   99
  4  \w   -118.00  -9.00   1.00    2.00    --  -41.88 -77.00 120.00  109
  5  \w   -115.00 -16.00   1.00    2.00    --  -41.88 -46.00   6.00   99
  6  \w   -118.00  -9.00   1.00    2.00    --  -41.88 -77.00-150.00  109
  7  \w   -118.00  -9.00   1.00    2.00    --  -41.88 -77.00  30.00  109
  8  \w      2.00  98.00   1.00    2.00    --   41.88-125.00-120.00   96
  9  \w    -30.00  70.00   1.00    2.00    --   41.88 -57.00-120.00  100
 10  \w      2.00  98.00   1.00    2.00    --   41.88-125.00  60.00   96
 11  \w     77.00 158.00   1.00    8.00    --  106.43  61.00 120.00   81
 12  \w     77.00 158.00   1.00    8.00    --  106.43  61.00  90.00   81
 13  \w     33.00 121.00   1.00    8.00    --  106.43-125.00 -90.00   88
 14  \w     33.00  77.00   1.00    8.00    --  106.43 -45.00 -60.00   44
 15  \w     77.00 158.00   1.00    8.00    --  106.43  61.00  30.00   81
 16  \w     77.00 158.00   1.00    8.00    --  106.43  61.00 -30.00   81
 17  \w     77.00 158.00   1.00    8.00    --  106.43  61.00 -90.00   81
 18  \w     77.00 158.00   1.00    8.00    --  106.43  61.00   0.00   81
 19  \w     74.00 158.00   1.00    8.00    --  106.43  77.00 120.00   84
 20  \w     33.00 121.00   1.00    8.00    --  106.43-125.00  60.00   88
 21  \w     74.00 158.00   1.00    8.00    --  106.43  77.00-120.00   84
 22  \w     77.00 158.00   1.00    8.00    --  106.43  61.00-120.00   81
 23  \w     33.00  77.00   1.00    8.00    --  106.43 -45.00  30.00   44
 24  \w     33.00  77.00   1.00    8.00    --  106.43 -45.00 120.00   44
 25  \w     33.00  77.00   1.00    8.00    --  106.43 -45.00-150.00   44
 26  \w     24.00 109.00   1.00    8.00    --  106.43 -94.00  60.00   85
 27  \w     77.00 158.00   1.00    8.00    --  106.43  61.00-180.00   81
 28  \w     33.00 121.00   1.00    8.00    --  106.43-125.00 -30.00   88
 29  \w     77.00 158.00   1.00    8.00    --  106.43  61.00 -60.00   81
 30  \w     74.00 158.00   1.00    8.00    --  106.43  77.00 150.00   84
 31  \w     74.00 158.00   1.00    8.00    --  106.43  77.00-180.00   84
 32  \w     74.00 158.00   1.00    8.00    --  106.43  77.00  60.00   84
 33  \w     74.00 158.00   1.00    8.00    --  106.43  77.00  90.00   84
 34  \w     74.00 158.00   1.00    8.00    --  106.43  77.00-150.00   84
 35  \w     74.00 133.00   1.00    8.00    --  106.43  77.00   0.00   59
 36  \w     74.00 143.00   1.00    8.00    --  106.43  77.00  30.00   69
 37  \w     77.00 104.00   1.00    8.00    --  106.43  61.00 150.00   27
 38  \w     74.00 158.00   1.00    8.00    --  106.43  77.00 -30.00   84
 39  \w     74.00 100.00   1.00    8.00    --  106.43  77.00 -90.00   26
 40  \w    104.00 145.00   1.00    8.00    --  106.43  77.00 -90.00   41
 41  \w     74.00 103.00   1.00    8.00    --  106.43  77.00 -60.00   29
 42  \w     77.00 158.00   1.00    8.00    --  106.43  61.00  60.00   81
 43  \w     77.00 157.00   1.00    8.00    --  106.43  61.00-150.00   80
 44  \w     39.00  80.00   1.00    8.00    --  106.43 -77.00  90.00   41
 45  \w    111.00 139.00   1.00    8.00    --  106.43 -77.00  90.00   28
 46  \w     42.00 114.00   1.00    8.00    --  106.43 -77.00 -60.00   72
 47  \w     24.00  98.00   1.00    8.00    --  106.43 -94.00 150.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0036878000
_diffrn_orient_matrix_UB_12      0.1006459000
_diffrn_orient_matrix_UB_13      0.0059028000
_diffrn_orient_matrix_UB_21      0.0782609000
_diffrn_orient_matrix_UB_22      -0.0314442000
_diffrn_orient_matrix_UB_23      0.0388073000
_diffrn_orient_matrix_UB_31      0.0731078000
_diffrn_orient_matrix_UB_32      0.0205013000
_diffrn_orient_matrix_UB_33      -0.0566637000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            104437
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.867
_diffrn_reflns_theta_min         3.392
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.118
_exptl_absorpt_correction_T_max  0.759
_exptl_absorpt_correction_T_min  0.536
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.37b (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       plate
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.179
_exptl_crystal_size_mid          0.129
_exptl_crystal_size_min          0.073
_refine_diff_density_max         1.450
_refine_diff_density_min         -1.575
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1137
_refine_ls_number_reflns         19481
_refine_ls_number_restraints     216
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0299P)^2^+7.6406P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0677
_refine_ls_wR_factor_ref         0.0714
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17385
_reflns_number_total             19481
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jz9b03002_si_002.cif
_cod_data_source_block           p150_sq
_cod_database_code               8000322
_chemical_oxdiff_formula         'C146 H182 Cl4 Ir4 N76 '
_chemical_oxdiff_usercomment     Shaftikov_Yersin_RED-79
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C34A-C33A \\sim C35A-C33A \\sim C36A-C33A \\sim C34-C33 \\sim C35-C33 \\sim
C36-C33 \\sim C90A-C87 ~
 C90-C87 \\sim C89A-C87 \\sim C89-C87 \\sim C88A-C87 \\sim C88-C87
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C33 \\sim C36 \\sim C34 \\sim C35 \\sim C35A \\sim C33A \\sim C36A \\sim C34A:
within 1.7A with sigma of 0.005 and sigma for terminal atoms of 0.005
C87 \\sim C88 \\sim C90 \\sim C89 \\sim C88A \\sim C89A \\sim C90A: within 1.7A
with sigma of 0.005 and sigma for terminal atoms of 0.005
4. Others
 Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C33A)=Sof(C36A)=Sof(H36D)=
 Sof(H36E)=Sof(H36F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(1)
 Sof(C33)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C34)=Sof(H34A)=Sof(H34B)=
 Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(1)
 Sof(C88A)=Sof(H88D)=Sof(H88E)=Sof(H88F)=Sof(C89A)=Sof(H89D)=Sof(H89E)=
 Sof(H89F)=Sof(C90A)=Sof(H90D)=Sof(H90E)=Sof(H90F)=1-FVAR(2)
 Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(H88C)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=
 Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=FVAR(2)
5.a Riding coordinates:
 C38(H38)
5.b Aromatic/amide H refined with riding coordinates:
 C48(H48), C50(H50), C55(H55), C40(H40), C41(H41), C77(H77), C75(H75), C2(H2),
 C17(H17), C83(H83), C52(H52), C72(H72), C31(H31), C15(H15), C86(H86), C5(H5),
 C84(H84), C22(H22), C12(H12), C96(H96), C62(H62), C3(H3), C68(H68), C53(H53),
 C10(H10), C9(H9), C4(H4), C11(H11), C85(H85), C26(H26), C8(H8), C70(H70),
 C28(H28), C95(H95), C30(H30), C71(H71), C24(H24), C63(H63), C64(H64), C23(H23),
  C69(H69), C65(H65), C94(H94), C25(H25), C29(H29), C92(H92), C93(H93)
5.c Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C45(H45A,H45B,H45C), C58(H58A,H58B,
 H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C88(H88A,H88B,H88C), C90(H90A,
 H90B,H90C), C89(H89A,H89B,H89C), C36(H36A,H36B,H36C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C35A(H35D,H35E,H35F), C36A(H36D,H36E,H36F), C34A(H34D,
 H34E,H34F), C88A(H88D,H88E,H88F), C89A(H89D,H89E,H89F), C90A(H90D,H90E,H90F),
 C99(H99A,H99B,H99C), C98(H98A,H98B,H98C), C97(H97A,H97B,H97C)
5.d Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O3(H3A)
;
_shelx_res_checksum              61271
_shelx_hkl_checksum              65597
_shelx_fab_checksum              46996
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-10-11
_olex2_date_sample_submission    2016-10-04
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems CryoStream 700'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder oil'
_olex2_submission_original_sample_id RED-79
_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 1.231
_oxdiff_exptl_absorpt_empirical_full_min 0.836