Pentacyclic fused diborepinium ions with carbene- and carbone-mediated deep-blue to red emission.
Hollister, Kimberly K.; Molino, Andrew; Le, VuongVy V; Jones, Nula; Smith, Wyatt J.; Müller, Peter; Dickie, Diane A.; Wilson, David J. D.; Gilliard, Jr, Robert J; Chemical science 15 (2024) 14358–14370; doi:10.1039/d4sc03835e

data_1572287
_publ_section_title
;
 Pentacyclic fused diborepinium ions with carbene- and carbone-mediated
 deep-blue to red emission.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              14358
_journal_page_last               14370
_journal_paper_doi               10.1039/d4sc03835e
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C96 H74 B2 P4, 2(C32 H12 B F24), 3(C H2 Cl2)'
_chemical_formula_sum            'C163 H104 B4 Cl6 F48 P4'
_chemical_formula_weight         3354.472
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-28 deposited with the CCDC.	2024-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                80.403(1)
_cell_angle_beta                 84.517(1)
_cell_angle_gamma                72.088(1)
_cell_formula_units_Z            1
_cell_length_a                   13.2079(5)
_cell_length_b                   15.4895(6)
_cell_length_c                   19.1541(6)
_cell_measurement_reflns_used    9492
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      31.463
_cell_measurement_theta_min      2.435
_cell_volume                     3672.4(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing.cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service V6.2.14'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing.data_reduction        'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing.structure_refinement  'SHELXL--2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing.structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 7.3910
_diffrn_detector_type            'Photon III'
_diffrn_measured_fraction_theta_full 0.9992
_diffrn_measured_fraction_theta_max 0.9969
_diffrn_measurement_device       'Kappa four--circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'one pinhole collimator 0.8 mm'
_diffrn_radiation_monochromator  'HELIOS double bounce multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.9992
_diffrn_reflns_Laue_measured_fraction_max 0.9969
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            222447
_diffrn_reflns_point_group_measured_fraction_full 0.9992
_diffrn_reflns_point_group_measured_fraction_max 0.9969
_diffrn_reflns.reduction_process narrow-frame
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         31.52
_diffrn_reflns_theta_min         1.88
_diffrn_source                   'micro-focus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\mS 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.276
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.7013
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1417 before and 0.0513 after correction.
The Ratio of minimum to maximum transmission is 0.9398.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.517
_exptl_crystal_description       plate
_exptl_crystal_F_000             1698.745
_exptl_crystal_size_max          0.665
_exptl_crystal_size_mid          0.445
_exptl_crystal_size_min          0.195
_refine_diff_density_max         0.8382
_refine_diff_density_min         -1.2281
_refine_diff_density_rms         0.0872
_refine_ls_d_res_high            0.6798
_refine_ls_d_res_low             10.8045
_refine_ls_goodness_of_fit_ref   1.0424
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    112
_refine_ls_number_parameters     1167
_refine_ls_number_reflns         24400
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.0379
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0473
_refine_ls_shift/su_max          0.0086
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0664P)^2^+2.9963P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1283
_refine_ls_wR_factor_ref         0.1342
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              19
_reflns_limit_h_min              -19
_reflns_limit_k_max              22
_reflns_limit_k_min              -22
_reflns_limit_l_max              28
_reflns_limit_l_min              0
_reflns_number_gt                21335
_reflns_number_total             24400
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4sc03835e2.cif
_cod_data_source_block           cdp_do
_cod_depositor_comments
'Adding full bibliography for 1572276--1572287.cif.'
_cod_database_code               1572287
_computing.bruker_data_scaling
'SADABS--2016/2 -- Bruker AXS area detector scaling and absorption correction'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C57-F1 \\sim C57-F2 \\sim C57-F3 \\sim C58-F4 \\sim C58-F5 \\sim C58-F6 \\sim
C67-F7 \\sim C67-F8 \\sim C67-
 F9 \\sim C68-F10 \\sim C68-F11 \\sim C68-F12 \\sim C77-F13 \\sim C77-F14 \\sim
C77-F15 \\sim C78-F16 \\sim C78-
 F17 \\sim C78-F18 \\sim C87-F19 \\sim C87-F20 \\sim C87-F21 \\sim C88-F22
\\sim C88-F23 \\sim C88-F24 ~
 C57-F1A \\sim C57-F2A \\sim C57-F3A \\sim C67-F7A \\sim C67-F8A \\sim C67-F9A
\\sim C68-F10A \\sim C68-
 F11A \\sim C68-F12A \\sim C78-F16A \\sim C78-F17A \\sim C78-F18A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F4-F5 \\sim F4-F6 \\sim F5-F6 \\sim F7-F8
\\sim F7-F9 \\sim F8-F9 \\sim F10-
 F11 \\sim F10-F12 \\sim F11-F12 \\sim F13-F14 \\sim F13-F15 \\sim F14-F15
\\sim F16-F17 \\sim F16-F18 ~
 F17-F18 \\sim F19-F20 \\sim F19-F21 \\sim F20-F21 \\sim F22-F23 \\sim F22-F24
\\sim F23-F24 \\sim F1A-F2A
 \\sim F1A-F3A \\sim F2A-F3A \\sim F7A-F8A \\sim F7A-F9A \\sim F8A-F9A \\sim
F10A-F11A \\sim F10A-F12A ~
 F11A-F12A \\sim F16A-F17A \\sim F16A-F18A \\sim F17A-F18A
 with sigma of 0.04
 C1S-Cl1S \\sim C1S-Cl2S \\sim C2S-Cl3S \\sim C2S-Cl4S \\sim C2S-Cl3S \\sim
C2S-Cl4S \\sim C2T-Cl4T ~
 C2T-Cl3T \\sim C2T-Cl4T
 with sigma of 0.02
 Cl1S-Cl2S \\sim Cl3S-Cl4S \\sim Cl3T-Cl4T
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C2S \\sim Cl3S \\sim Cl4S \\sim C2T \\sim Cl3T \\sim Cl4T: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
F1 \\sim F2 \\sim F3 \\sim F1A \\sim F2A \\sim F3A \\sim F4 \\sim F5 \\sim F6
\\sim F7 \\sim F8 \\sim F9 \\sim F7A \\sim F8A \\sim F9A \\sim F10 \\sim F11
\\sim F12 \\sim F10A \\sim F11A \\sim F12A \\sim F13 \\sim F14 \\sim F15 \\sim
F16 \\sim F17 \\sim F18 \\sim F16A \\sim F17A \\sim F18A \\sim F19 \\sim F20
\\sim F21 \\sim F22 \\sim F23 \\sim F24: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C2S, Cl3S, Cl4S, C2T, Cl3T, Cl4T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F2, F3, F1A, F2A, F3A, F4, F5, F6, F7, F8, F9, F7A, F8A, F9A, F10, F11,
 F12, F10A, F11A, F12A, F13, F14, F15, F16, F17, F18, F16A, F17A, F18A, F19,
 F20, F21, F22, F23, F24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C2T)=Sof(H2Ta)=Sof(H2Tb)=Sof(Cl3T)=Sof(Cl4T)=0.5*(1-FVAR(2))
 Sof(C2S)=Sof(H2Sa)=Sof(H2Sb)=Sof(Cl3S)=Sof(Cl4S)=0.5*FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(4)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(4)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(5)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C1S(H1Sa,H1Sb), C2S(H2Sa,H2Sb), C2T(H2Ta,H2Tb)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42),
  C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C52(H52), C54(H54),
 C56(H56), C62(H62), C64(H64), C66(H66), C72(H72), C74(H74), C76(H76), C82(H82),
  C84(H84), C86(H86)
;
_olex2_submission_special_instructions 'No special instructions were received'