Persistent Dimer Emission in Thermally Activated Delayed Fluorescence Materials.
Etherington, Marc K.; Kukhta, Nadzeya A.; Higginbotham, Heather F.; Danos, Andrew; Bismillah, Aisha N.; Graves, David R.; McGonigal, Paul R.; Haase, Nils; Morherr, Antonia; Batsanov, Andrei S.; Pflumm, Christof; Bhalla, Vandana; Bryce, Martin R.; Monkman, Andrew P.; The journal of physical chemistry. C, Nanomaterials and interfaces 123 (2019) 11109–11117; doi:10.1021/acs.jpcc.9b01458

data_4003415
_publ_section_title
;
 Persistent Dimer Emission in Thermally Activated Delayed Fluorescence
 Materials.
;
_journal_issue                   17
_journal_name_full
'The journal of physical chemistry. C, Nanomaterials and interfaces'
_journal_page_first              11109
_journal_page_last               11117
_journal_paper_doi               10.1021/acs.jpcc.9b01458
_journal_volume                  123
_journal_year                    2019
_chemical_formula_moiety         'C56 H31 Br N6, 2(C2 H3 N)'
_chemical_formula_sum            'C60 H37 Br N8'
_chemical_formula_weight         949.88
_chemical_name_systematic
'2-(3-bromocarbazole-9-yl)-1,3,5-trikis(carbazol-9-yl)-4,6-dicyanobenzene, acetonitrile solvate'
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-15
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.3397(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9331(3)
_cell_length_b                   19.6323(6)
_cell_length_c                   22.4761(6)
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      71.27
_cell_measurement_theta_min      3.02
_cell_volume                     4712.9(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker, 2017)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      200.0
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '3-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0758
_diffrn_reflns_av_unetI/netI     0.0707
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            57821
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.993
_diffrn_reflns_theta_min         3.019
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.579
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8106
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0905 before and 0.0558 after correction.
The Ratio of minimum to maximum transmission is 0.8106.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear greenish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             1952
_exptl_crystal_recrystallization_method 'from acetonitrile'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.391
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.069
_refine_ls_extinction_coef       0.00144(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     604
_refine_ls_number_reflns         8763
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.1053
_refine_ls_R_factor_gt           0.0797
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0001P)^2^+13.4690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1871
_refine_ls_wR_factor_ref         0.1999
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6359
_reflns_number_total             8763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            4CzIPNBr-200K.cif
_cod_data_source_block           4CzIPNBr-18s101
_cod_database_code               4003415
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.600
_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. Uiso/Uaniso restraints and constraints
Uiso(C55) = Uiso(C55A)
Uiso(C56A) = Uiso(C56)
Uiso(C54) = Uiso(C54A)
Uiso(C53) = Uiso(C53A)
Uiso(C52) = Uiso(C52A)
Uiso(C51) = Uiso(C51A)
Uiso(N5) = Uiso(N5A)
Uiso(C50A) = Uiso(C50)
Uiso(C45) = Uiso(C45A)
Uiso(C49) = Uiso(C49A)
Uiso(C48) = Uiso(C48A)
Uiso(C47) = Uiso(C47A)
Uiso(C46) = Uiso(C46A)
3. Same fragment restrains
{N5, C45, C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56} sigma for 1-2:
0.02, 1-3: 0.04
as
{N5A, C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A, C53A, C54A, C55A, C56A}
4. Others
 Sof(N5A)=Sof(C45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=Sof(C48A)=
 Sof(H48A)=Sof(C49A)=Sof(H49A)=Sof(C50A)=Sof(C51A)=Sof(C52A)=Sof(H52A)=
 Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=1-FVAR(1)
 Sof(N5)=Sof(C45)=Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48)=
 Sof(C49)=Sof(H49)=Sof(C50)=Sof(C51)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53)=
 Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=Sof(C56)=FVAR(1)
 Fixed Sof: Br1(0.85) Br1A(0.15)
5.a Riding coordinates:
 C41(H41)
5.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17), C18(H18),
 C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C28(H28), C29(H29), C30(H30),
  C31(H31), C34(H34), C35(H35), C37(H37), C40(H40), C42(H42), C43(H43),
 C46(H46), C47(H47), C48(H48), C49(H49), C52(H52), C53(H53), C54(H54), C55(H55),
  C46A(H46A), C47A(H47A), C48A(H48A), C49A(H49A), C52A(H52A), C53A(H53A),
 C54A(H54A), C55A(H55A)
5.c Idealised Me refined as rotating group:
 C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              45635
_shelx_hkl_checksum              52617
_olex2_submission_special_instructions 'No special instructions were received'