Stable N-heterocyclic carbene (NHC) cyclometalated (C^C) gold(iii) complexes as blue‒blue green phosphorescence emitters
von Arx, Tobias; Szentkuti, Alexander; Zehnder, Thomas N.; Blacque, Olivier; Venkatesan, Koushik; Journal of Materials Chemistry C 5 (2017) 3765–; doi:10.1039/C6TC05551F

data_7236472
_publ_section_title
;
 Stable N-heterocyclic carbene (NHC) cyclometalated (C^C) gold(iii)
 complexes as blue--blue green phosphorescence emitters
;
_journal_issue                   15
_journal_name_full               'Journal of Materials Chemistry C'
_journal_page_first              3765
_journal_paper_doi               10.1039/C6TC05551F
_journal_volume                  5
_journal_year                    2017
_chemical_formula_moiety         '4(C30 H15 Au F6 N2 O), C H2 Cl2'
_chemical_formula_sum            'C121 H62 Au4 Cl2 F24 N8 O4'
_chemical_formula_weight         3006.55
_chemical_name_systematic
'(3,4-dibenzofurandiyl(3-methyl-1H-imidazol-2-ylidene))-pentafluorophenyl-(4-fluorophenylethynyl)-gold(iii) dichloromethane solvate 4:1'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-11-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-12-14 deposited with the CCDC.
2017-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.587(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.9429(4)
_cell_length_b                   13.3830(4)
_cell_length_c                   27.7426(13)
_cell_measurement_reflns_used    14699
_cell_measurement_temperature    183(1)
_cell_measurement_theta_max      75.8
_cell_measurement_theta_min      3.3
_cell_volume                     5537.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      183(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1900
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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   -117.00 -14.60   0.80    5.00    --  -40.39 -37.00  30.00  128
  2  \w    -61.00 -33.00   0.80    5.00    --  -40.39  37.00  90.00   35
  3  \w     37.00  90.60   0.80    5.00    --   40.39-125.00  90.00   67
  4  \w      8.00  73.60   0.80    5.00    --   40.39 -99.00 -90.00   82
  5  \w      2.00  43.60   0.80    5.00    --   40.39 -99.00   0.00   52
  6  \w     12.00  39.20   0.80    5.00    --   40.39 -99.00-120.00   34
  7  \w     40.00  67.20   0.80   20.00    --  113.00 -45.00 150.00   34
  8  \w    135.00 163.00   0.80   20.00    --  113.00  61.00  90.00   35
  9  \w    127.60 178.00   0.80   20.00    --  113.00  35.00  -7.06   63
 10  \w     84.00 144.00   0.80   20.00    --  113.00  57.00 161.31   75
 11  \w     88.00 103.20   0.80   20.00    --  113.00 -77.00-180.00   19
 12  \w    101.00 129.00   0.80   20.00    --  113.00 111.00  90.00   35
 13  \w     83.00 123.00   0.80   20.00    --  113.00  66.00   3.30   50
 14  \w     29.00  95.40   0.80   20.00    --  113.00 -94.00-150.00   83
 15  \w    110.00 142.80   0.80   20.00    --  113.00 -61.00-150.00   41
 16  \w     84.00 111.20   0.80   20.00    --  113.00  61.00  90.00   34
 17  \w     65.00  92.20   0.80   20.00    --  113.00 -61.00-150.00   34
 18  \w     59.00 107.00   0.80   20.00    --  113.00 178.00  60.00   60
 19  \w     87.00 118.20   0.80   20.00    --  113.00  58.00 134.11   39
 20  \w     74.00 144.40   0.80   20.00    --  113.00 -69.00 -16.56   88
 21  \w     87.00 151.00   0.80   20.00    --  113.00  50.00 124.58   80
 22  \w     85.00 101.80   0.80   20.00    --  113.00-111.00 -30.00   21
 23  \w    148.00 176.00   0.80   20.00    --  113.00  33.00-144.54   35
 24  \w     70.00 105.20   0.80   20.00    --  113.00 -15.00-180.00   44
 25  \w    125.00 173.00   0.80   20.00    --  113.00 -15.00-180.00   60
 26  \w     60.00  87.20   0.80   20.00    --  113.00 -94.00-180.00   34
 27  \w     36.00  72.00   0.80   20.00    --  113.00-111.00-180.00   45
 28  \w     94.00 121.20   0.80   20.00    --  113.00  61.00-180.00   34
 29  \w    152.00 178.40   0.80   20.00    --  113.00  61.00-180.00   33
 30  \w     84.00 112.00   0.80   20.00    --  113.00  61.00 -60.00   35
 31  \w     83.00 139.00   0.80   20.00    --  113.00 -45.00 150.00   70
 32  \w     64.00  95.20   0.80   20.00    --  113.00-111.00 120.00   39
 33  \w     57.00  84.20   0.80   20.00    --  113.00 178.00-180.00   34
 34  \w     90.00 125.20   0.80   20.00    --  113.00  45.00 -30.00   44
 35  \w     46.00  73.20   0.80   20.00    --  113.00 -45.00  30.00   34
 36  \w     41.00  73.00   0.80   20.00    --  113.00 -94.00-120.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999, Acta A55, 543-557)'
_diffrn_orient_matrix_UB_11      -0.0838985000
_diffrn_orient_matrix_UB_12      -0.0312416000
_diffrn_orient_matrix_UB_13      0.0258527000
_diffrn_orient_matrix_UB_21      0.0321277000
_diffrn_orient_matrix_UB_22      0.0632238000
_diffrn_orient_matrix_UB_23      0.0441529000
_diffrn_orient_matrix_UB_31      -0.0510591000
_diffrn_orient_matrix_UB_32      0.0910574000
_diffrn_orient_matrix_UB_33      -0.0217386000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0583
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            39541
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.247
_diffrn_reflns_theta_min         3.192
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.036
_exptl_absorpt_correction_T_max  0.816
_exptl_absorpt_correction_T_min  0.231
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.803
_exptl_crystal_description       needle
_exptl_crystal_F_000             2884
_exptl_crystal_preparation       ', Luminescent'
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.360
_refine_diff_density_min         -2.580
_refine_diff_density_rms         0.211
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     715
_refine_ls_number_reflns         10053
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0837
_refine_ls_R_factor_gt           0.0732
_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^)+(0.1291P)^2^+32.9302P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2042
_refine_ls_wR_factor_ref         0.2139
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8391
_reflns_number_total             10053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6tc05551f2.cif
_cod_data_source_block           2c_CCDC-1497784
_cod_database_code               7236472
_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
 Cl1-C61 = Cl2-C61 = Cl3-C62 = Cl4-C62
 1.76 with sigma of 0.01
 C41A-C42A = C42A-C43A = C43A-C44A = C44A-C45A = C45A-C46A = C46A-C41A
 1.4 with sigma of 0.005
 C41B-C42B = C42B-C43B = C43B-C44B = C44B-C45B = C45B-C46B = C46B-C41B
 1.4 with sigma of 0.005
 Cl3-Cl4
 2.9 with sigma of 0.01
 C38-C41A \\sim C38-C41B
 with sigma of 0.005
 O2A-C46A \\sim O2A-C39 \\sim O2B-C39 \\sim O2B-C46B
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1) = Uanis(Cl2) = Uanis(C61) = Uanis(Cl4) = Uanis(Cl3) = Uanis(C62)
Uanis(O2B) = Uanis(C37) = Uanis(C38) = Uanis(C39) = Uanis(C46A) = Uanis(C45A) =
Uanis(C44A) = Uanis(C43A) = Uanis(C42A) = Uanis(C41A) = Uanis(C46B) =
Uanis(C45B) = Uanis(C44B) = Uanis(C43B) = Uanis(C42B) = Uanis(C41B) = Uanis(O2A)
4. Rigid body (RIGU) restrains
 C49, C50, C51, C52, C53, C54
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Cl1, Cl2, C61
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Cl1, Cl2, C61, C62, Cl3, Cl4
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C41A, C42A, C43A, C44A, C45A, C46A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O2B)=Sof(C41B)=Sof(C42B)=Sof(H42B)=Sof(C43B)=Sof(H43B)=Sof(C44B)=
 Sof(H44B)=Sof(C45B)=Sof(H45B)=Sof(C46B)=1-FVAR(1)
 Sof(O2A)=Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=
 Sof(H44A)=Sof(C46A)=Sof(C45A)=Sof(H45A)=FVAR(1)
 Fixed Sof: Cl1(0.25) Cl2(0.25) C61(0.25) H61A(0.25) H61B(0.25) C62(0.25)
 H62A(0.25) H62B(0.25) Cl3(0.25) Cl4(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C62(H62A,H62B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C12(H12), C13(H13), C14(H14), C15(H15),
 C20(H20), C21(H21), C23(H23), C24(H24), C32(H32), C33(H33), C36(H36), C37(H37),
  C50(H50), C51(H51), C53(H53), C54(H54), C42A(H42A), C43A(H43A), C44A(H44A),
 C45A(H45A), C42B(H42B), C43B(H43B), C44B(H44B), C45B(H45B)
6.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C34(H34A,H34B,H34C)
;
_shelx_res_checksum              64318
_shelx_hkl_checksum              1032
_shelx_shelxl_version_number     2014/7