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_4003413
_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 H32 N6, 3.5(C3 H6 O)'
_chemical_formula_sum            'C66.5 H53 N6 O3.5'
_chemical_formula_weight         992.15
_chemical_name_systematic
'2,3,5,6-tetrakis(carbazol-9-yl)-1,4-dicyanobenzene, acetone 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   geom
_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                 101.5220(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.5010(5)
_cell_length_b                   23.4890(9)
_cell_length_c                   17.2129(7)
_cell_measurement_reflns_used    9944
_cell_measurement_temperature    120
_cell_measurement_theta_max      25.806
_cell_measurement_theta_min      2.469
_cell_volume                     5348.6(4)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX3 v.2016.1-0 (Bruker, 2016)'
_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 2018/3 multi-CPU version (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS 2013/1 (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '3-circle area detector diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0366
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            73332
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.113
_exptl_absorpt_coefficient_mu    0.077
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9645
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1105 before and 0.0421 after correction.
The Ratio of minimum to maximum transmission is 0.9645.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2088
_exptl_crystal_recrystallization_method
'from acetone/hexane/DCM, 2nd Oswald stage'
_exptl_crystal_size_max          0.376
_exptl_crystal_size_mid          0.366
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.500
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.0051(7)
_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, 2015)'
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     811
_refine_ls_number_reflns         9415
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0757
_refine_ls_R_factor_gt           0.0575
_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^)+(0.0758P)^2^+3.8968P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1503
_refine_ls_wR_factor_ref         0.1636
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7366
_reflns_number_total             9415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            4CzIPN-ac.cif
_cod_data_source_block           4CzIPN-ac-18s437
_cod_original_formula_sum        'C66.50 H53 N6 O3.50'
_cod_database_code               4003413
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.972
_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
 C6S'-C4S' \\sim C5S'-C4S' \\sim C5S-C4S \\sim C6S-C4S
 with sigma of 0.02
 O2S-C4S' \\sim O2S-C4S
 with sigma of 0.02
 C10S-C12S \\sim C11S-C10S \\sim C13S-C15S \\sim C14S-C13S
 with sigma of 0.02
 O4S-C10S \\sim O4S-C13S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C40') = Uiso(C41)
Uanis(N4) = Uanis(N4')
4. Rigid body (RIGU) restrains
 O2S, C4S, C6S, C5S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2S, C4S', C6S', C5S'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{N4', C33', C34', C35', C36', C37', C38', C39', C40', C41', C42', C43', C44'}
sigma for 1-2: 0.02, 1-3: 0.04
as
{N4, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44}
6. Others
 Sof(N4)=Sof(C33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=
 Sof(C37)=Sof(H37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(H40)=Sof(C41)=Sof(H41)=
 Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=Sof(C44)=1-FVAR(1)
 Sof(N4')=Sof(C33')=Sof(C34')=Sof(H34')=Sof(C35')=Sof(H35')=Sof(C36')=
 Sof(H36')=Sof(C37')=Sof(H37')=Sof(C38')=Sof(C39')=Sof(C40')=Sof(H40')=
 Sof(C41')=Sof(H41')=Sof(C42')=Sof(H42')=Sof(C43')=Sof(H43')=Sof(C44')=FVAR(1)
 Fixed Sof: C11S(0.5) H11A(0.5) H11B(0.5) H11C(0.5) C9S(0.5) H9SA(0.5)
 H9SB(0.5) H9SC(0.5) C14S(0.5) H14A(0.5) H14B(0.5) H14C(0.5) C7S(0.5) O3S(0.5)
 C10S(0.5) C12S(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C8S(0.5) H8SA(0.5) H8SB(0.5)
 H8SC(0.5) C4S(0.5) C5S(0.5) H5SA(0.5) H5SB(0.5) H5SC(0.5) C6S(0.5) H6SA(0.5)
 H6SB(0.5) H6SC(0.5) C6S'(0.5) H6SD(0.5) H6SE(0.5) H6SF(0.5) C4S'(0.5)
 C5S'(0.5) H5SD(0.5) H5SE(0.5) H5SF(0.5) C13S(0.5) C15S(0.5) H15A(0.5)
 H15B(0.5) H15C(0.5)
7.a Me refined with riding coordinates:
 C11S(H11A,H11B,H11C), C9S(H9SA,H9SB,H9SC), C14S(H14A,H14B,H14C), C12S(H12A,
 H12B,H12C), C8S(H8SA,H8SB,H8SC), C5S(H5SA,H5SB,H5SC), C6S(H6SA,H6SB,H6SC),
 C6S'(H6SD,H6SE,H6SF), C5S'(H5SD,H5SE,H5SF), C15S(H15A,H15B,H15C)
7.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), C46(H46), C47(H47), C48(H48), C49(H49), C52(H52), C53(H53),
 C54(H54), C55(H55), C34'(H34'), C35'(H35'), C36'(H36'), C37'(H37'), C40'(H40'),
  C41'(H41'), C42'(H42'), C43'(H43'), C34(H34), C35(H35), C36(H36), C37(H37),
 C40(H40), C41(H41), C42(H42), C43(H43)
7.c Idealised Me refined as rotating group:
 C2S(H2SA,H2SB,H2SC), C3S(H3SA,H3SB,H3SC)
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_shelx_res_checksum              36215
_shelx_hkl_checksum              3827
_olex2_submission_special_instructions 'No special instructions were received'