Delayed Blue Fluorescence via Upper-Triplet State Crossing from C‒C Bonded Donor‒Acceptor Charge Transfer Molecules with Azatriangulene Cores
Ward, Jonathan S.; Kukhta, Nadzeya A.; dos Santos, Paloma L.; Congrave, Daniel G.; Batsanov, Andrei S.; Monkman, Andrew P.; Bryce, Martin R.; Chemistry of Materials 31 (2019) 6684–; doi:10.1021/acs.chemmater.9b01184

data_4002961
_publ_section_title
;
 Delayed Blue Fluorescence via Upper-Triplet State Crossing from C--C
 Bonded Donor--Acceptor Charge Transfer Molecules with Azatriangulene
 Cores
;
_journal_issue                   17
_journal_name_full               'Chemistry of Materials'
_journal_page_first              6684
_journal_paper_doi               10.1021/acs.chemmater.9b01184
_journal_volume                  31
_journal_year                    2019
_chemical_formula_moiety         'C81 H45 F9 N4, 3(C2 H3 N)'
_chemical_formula_sum            'C87 H54 F9 N7'
_chemical_formula_weight         1368.37
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   constr
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-03-10
_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                 105.9246(14)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   23.7795(7)
_cell_length_b                   31.6796(9)
_cell_length_c                   28.2823(8)
_cell_measurement_reflns_used    9913
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      50.880
_cell_measurement_theta_min      2.383
_cell_volume                     20488.1(10)
_computing_cell_refinement       'SAINT v8.38A (Bruker AXS, 2016)'
_computing_data_collection       'APEX3 v.2017.3_0 (Bruker AXS, 2017)'
_computing_data_reduction        'SAINT v8.38A (Bruker AXS, 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 (Sheldrick, 2015)'
_computing_structure_solution    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'Bruker PHOTON 100 CMOS'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       '3-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2646
_diffrn_reflns_av_unetI/netI     0.1692
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            281239
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.000
_diffrn_reflns_theta_min         2.141
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\mS microsource'
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9220
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker, 2016) was used for absorption correction.
wR2(int) was 0.0818 before and 0.0713 after correction.
The Ratio of minimum to maximum transmission is 0.9220.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.331
_exptl_crystal_description       brick
_exptl_crystal_F_000             8472
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.392
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.077
_refine_ls_extinction_coef       0.00083(3)
_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   0.963
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2818
_refine_ls_number_reflns         37252
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      0.963
_refine_ls_R_factor_all          0.2054
_refine_ls_R_factor_gt           0.0875
_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^)+(0.1151P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1951
_refine_ls_wR_factor_ref         0.2584
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15336
_reflns_number_total             37252
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            2b.cif
_cod_data_source_block           2b_18s454
_cod_database_code               4002961
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.918
_computing_bruker_data_scaling   'SADABS V2012/1 (Bruker AXS Inc.)'
_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
 C8T-C7T
 1.5 with sigma of 0.02
 C7T-N4T
 1.15 with sigma of 0.02
 N4-C69 \\sim N4E-C69E \\sim N4A-C69A \\sim N4D-C69D
 with sigma of 0.002
 C65A-C69A \\sim C65A-C69D \\sim C65-C69 \\sim C65-C69E
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uiso(N4T) = Uiso(C7T) = Uiso(C8T)
4. Others
 Sof(N4E)=Sof(C69E)=1-FVAR(1)
 Sof(N4)=Sof(C69)=FVAR(1)
 Fixed Sof: N4A(0.5) N4D(0.5) C69A(0.5) C69D(0.5) N1S(0.85) N2S(0.85)
 N3S(0.85) C1S(0.85) C2S(0.85) H2SA(0.85) H2SB(0.85) H2SC(0.85) C3S(0.85)
 C5S(0.85) C6S(0.85) H6SA(0.85) H6SB(0.85) H6SC(0.85) N4S(0.75) C7S(0.75)
 C8S(0.75) H8SA(0.75) H8SB(0.75) H8SC(0.75) N5S(0.75) C9S(0.75) C10S(0.75)
 H10A(0.75) H10B(0.75) H10C(0.75) N9S(0.75) C17S(0.75) C18S(0.75) H18C(0.75)
 H18D(0.75) H18E(0.75) C6T(0.15) N1T(0.15) C8T(0.25) H8TA(0.25) H8TB(0.25)
 H8TC(0.25) N4T(0.25) C7T(0.25) N9T(0.15) C1T(0.15) C17T(0.25) C10T(0.2)
 C18T(0.25)
5.a Riding coordinates:
 C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C6S(H6SA,H6SB,H6SC), C8S(H8SA,H8SB,
 H8SC), C10S(H10A,H10B,H10C), C12S(H12A,H12B,H12C), C14S(H14A,H14B,H14C),
 C16S(H16C,H16D,H16E), C18S(H18C,H18D,H18E), C8T(H8TA,H8TB,H8TC)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C11(H11), C13(H13), C16(H16), C18(H18), C24(H24), C26(H26),
 C27(H27), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38),
  C39(H39), C40(H40), C41(H41), C44(H44), C46(H46), C47(H47), C51(H51),
 C52(H52), C53(H53), C54(H54), C55(H55), C57(H57), C58(H58), C59(H59), C60(H60),
  C61(H61), C64(H64), C66(H66), C67(H67), C71(H71), C72(H72), C73(H73),
 C74(H74), C75(H75), C77(H77), C78(H78), C79(H79), C80(H80), C81(H81), C3A(H3A),
  C5A(H5A), C11A(H11A), C13A(H13A), C16A(H16A), C18A(H18A), C24A(H24A),
 C26A(H26A), C27A(H27A), C31A(H31A), C32A(H32A), C33A(H33A), C34A(H34A),
 C35A(H35A), C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A), C41A(H41A),
 C44A(H44A), C46A(H46A), C47A(H47A), C51A(H51A), C52A(H52A), C53A(H53A),
 C54A(H54A), C55A(H55A), C57A(H57A), C58A(H58A), C59A(H59A), C60A(H60A),
 C61A(H61A), C64A(H64A), C66A(H66A), C67A(H67A), C71A(H71A), C72A(H72A),
 C73A(H73A), C74A(H74A), C75A(H75A), C77A(H77A), C78A(H78A), C79A(H79A),
 C80A(H80A), C81A(H81A), C3B(H3B), C5B(H5B), C11B(H11B), C13B(H13B), C16B(H16B),
  C18B(H18B), C24B(H24B), C26B(H26B), C27B(H27B), C31B(H31B), C32B(H32B),
 C33B(H33B), C34B(H34B), C35B(H35B), C37B(H37B), C38B(H38B), C39B(H39B),
 C40B(H40B), C41B(H41B), C44B(H44B), C46B(H46B), C47B(H47B), C51B(H51B),
 C52B(H52B), C53B(H53B), C54B(H54B), C55B(H55B), C57B(H57B), C58B(H58B),
 C59B(H59B), C60B(H60B), C61B(H61B), C64B(H64B), C66B(H66B), C67B(H67B),
 C71B(H71B), C72B(H72B), C73B(H73B), C74B(H74B), C75B(H75B), C77B(H77B),
 C78B(H78B), C79B(H79B), C80B(H80B), C81B(H81B)
;
_shelx_res_checksum              29958
_shelx_hkl_checksum              3764