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_1572282
_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         'C68 H70 B2 N8, 2(C32 H12 B F24), 2(C4 H10 O1)'
_chemical_formula_sum            'C140 H114 B4 F48 N8 O2'
_chemical_formula_weight         2895.63
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-03-26
_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                77.797(2)
_cell_angle_beta                 84.084(2)
_cell_angle_gamma                73.633(2)
_cell_formula_units_Z            1
_cell_length_a                   11.0428(5)
_cell_length_b                   16.5514(8)
_cell_length_c                   19.2623(8)
_cell_measurement_reflns_used    9905
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.25
_cell_measurement_theta_min      2.25
_cell_volume                     3298.1(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX3 v2017.3.0 (Bruker-AXS, 2017)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2015 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 7.4
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0861
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            56332
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.521
_diffrn_reflns_theta_min         1.924
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.133
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6892
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0963 before and 0.0563 after correction.
The Ratio of minimum to maximum transmission is 0.9237.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1478
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.362
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.947
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1202
_refine_ls_number_reflns         19780
_refine_ls_number_restraints     3917
_refine_ls_restrained_S_all      0.914
_refine_ls_R_factor_all          0.1138
_refine_ls_R_factor_gt           0.0629
_refine_ls_shift/su_max          0.071
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0603P)^2^+3.2381P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1383
_refine_ls_wR_factor_ref         0.1654
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13079
_reflns_number_total             19780
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03835e2.cif
_cod_data_source_block           cdc
_cod_depositor_comments
'Adding full bibliography for 1572276--1572287.cif.'
_cod_database_code               1572282
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.959
_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
 C47-F1 \\sim C47-F2 \\sim C47-F3 \\sim C48-F4 \\sim C48-F5 \\sim C48-F6 \\sim
C48A-F4A \\sim C48A-F5A ~
 C48A-F6A \\sim C57-F7 \\sim C57-F8 \\sim C57-F9 \\sim C58-F10 \\sim C58-F11
\\sim C58-F12 \\sim C57-F7A ~
 C57-F8A \\sim C57-F9A \\sim C58A-F10A \\sim C58A-F11A \\sim C58A-F12A \\sim
C58B-F10B \\sim C58B-F11B
 \\sim C58B-F12B \\sim C67-F13 \\sim C67-F14 \\sim C67-F15 \\sim C68-F16 \\sim
C68-F17 \\sim C68-F18 \\sim C68A-
 F16A \\sim C68A-F17A \\sim C68A-F18A \\sim C77-F19 \\sim C77-F20 \\sim C77-F21
\\sim C78-F22 \\sim C78-F23
 \\sim C78-F24 \\sim C77A-F19A \\sim C77A-F20A \\sim C77A-F21A
 with sigma of 0.02
 C43-C47 \\sim C45-C48 \\sim C53-C57 \\sim C55-C58 \\sim C63-C67 \\sim C65-C68
\\sim C73-C77 \\sim C75-C78
 \\sim C45-C48A \\sim C55-C58A \\sim C55-C58B \\sim C65-C68A \\sim C73-C77A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F4-F5 \\sim F4-F6 \\sim F5-F6 \\sim
F4A-F5A \\sim F4A-F6A \\sim F5A-F6A ~
 F7-F8 \\sim F7-F9 \\sim F8-F9 \\sim F10-F11 \\sim F10-F12 \\sim F11-F12 \\sim
F7A-F8A \\sim F7A-F9A \\sim F8A-
 F9A
 with sigma of 0.04
 C43-F1 \\sim C43-F2 \\sim C43-F3 \\sim C45-F4 \\sim C45-F5 \\sim C45-F6 \\sim
C45-F4A \\sim C45-F5A \\sim C45-
 F6A \\sim C53-F7 \\sim C53-F8 \\sim C53-F9 \\sim C55-F10 \\sim C55-F11 \\sim
C55-F12 \\sim C53-F7A \\sim C53-
 F8A \\sim C53-F9A \\sim C55-F10A \\sim C55-F11A \\sim C55-F12A \\sim C55-F10B
\\sim C55-F11B \\sim C55-
 F12B \\sim C63-F13 \\sim C63-F14 \\sim C63-F15 \\sim C65-F16 \\sim C65-F17
\\sim C65-F18 \\sim C65-F16A ~
 C65-F17A \\sim C65-F18A \\sim C73-F19 \\sim C73-F20 \\sim C73-F21 \\sim
C75-F22 \\sim C75-F23 \\sim C75-
 F24 \\sim C73-F19A \\sim C73-F20A \\sim C73-F21A
 with sigma of 0.04
 O1S-C1S \\sim O1S-C3S \\sim O1T-C1T \\sim O1T-C3T
 with sigma of 0.02
 C1S-C2S \\sim C3S-C4S \\sim C1T-C2T \\sim C3T-C4T
 with sigma of 0.02
 O1S-C2S \\sim O1S-C4S \\sim O1T-C2T \\sim O1T-C4T
 with sigma of 0.04
 C1S-C3S \\sim C1T-C3T
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
B2 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim
F1 \\sim F2 \\sim F3 \\sim C48 \\sim F4 \\sim F5 \\sim F6 \\sim C48A \\sim F4A
\\sim F5A \\sim F6A \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56
\\sim C57 \\sim F7 \\sim F8 \\sim F9 \\sim F7A \\sim F8A \\sim F9A \\sim C58
\\sim F10 \\sim F11 \\sim F12 \\sim C58A \\sim F10A \\sim F11A \\sim F12A \\sim
C58B \\sim F10B \\sim F11B \\sim F12B \\sim C61 \\sim C62 \\sim C63 \\sim C64
\\sim C65 \\sim C66 \\sim C67 \\sim F13 \\sim F14 \\sim F15 \\sim F13A \\sim
F14A \\sim F15A \\sim C68 \\sim F16 \\sim F17 \\sim F18 \\sim C68A \\sim F16A
\\sim F17A \\sim F18A \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim
C76 \\sim C77 \\sim F19 \\sim F20 \\sim F21 \\sim C77A \\sim F19A \\sim F20A
\\sim F21A \\sim C78 \\sim F22 \\sim F23 \\sim F24: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O1S \\sim C1S \\sim C2S \\sim C3S \\sim C4S \\sim O1T \\sim C1T \\sim C2T \\sim
C3T \\sim C4T: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
Uanis(C48) = Uanis(C48A)
Uanis(C58) = Uanis(C58A) = Uanis(C58B)
Uanis(C68) = Uanis(C68A)
4. Rigid body (RIGU) restrains
 B2, C41, C42, C43, C44, C45, C46, C47, F1, F2, F3, C48, F4, F5, F6, C48A, F4A,
  F5A, F6A, C51, C52, C53, C54, C55, C56, C57, F7, F8, F9, F7A, F8A, F9A, C58,
 F10, F11, F12, C58A, F10A, F11A, F12A, C58B, F10B, F11B, F12B, C61, C62, C63,
 C64, C65, C66, C67, F13, F14, F15, F13A, F14A, F15A, C68, F16, F17, F18, C68A,
 F16A, F17A, F18A, C71, C72, C73, C74, C75, C76, C77, F19, F20, F21, C77A, F19A,
  F20A, F21A, C78, F22, F23, F24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1S, C1S, C2S, C3S, C4S, O1T, C1T, C2T, C3T, C4T
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(C58)+Sof(F10)+Sof(F11)+Sof(F12)]+1*[Sof(C58A)+Sof(F10A)+Sof(F11A)+
 Sof(F12A)]+1*[Sof(C58B)+Sof(F10B)+Sof(F11B)+Sof(F12B)]=1 with esd of 0
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(1)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(1)
 Sof(C58)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Sof(C58A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(3)
 Sof(C58B)=Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(4)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(5)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(5)
 Sof(C68A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(6)
 Sof(C68)=Sof(F16)=Sof(F17)=Sof(F18)=FVAR(6)
 Sof(C77A)=Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(7)
 Sof(C77)=Sof(F19)=Sof(F20)=Sof(F21)=FVAR(7)
 Sof(O1T)=Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(H2TC)=
 Sof(C3T)=Sof(H3TA)=Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=Sof(H4TC)=1-FVAR(8)
 Sof(O1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=
 Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=FVAR(8)
 Sof(C48A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(9)
 Sof(C48)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(9)
6.a Ternary CH refined with riding coordinates:
 C21(H21), C32(H32)
6.b Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C3S(H3SA,H3SB), C1T(H1TA,H1TB), C3T(H3TA,H3TB)
6.c Me refined with riding coordinates:
 C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C2T(H2TA,H2TB,H2TC), C4T(H4TA,H4TB,
 H4TC)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17),
 C18(H18), C19(H19), C27(H27), C28(H28), C29(H29), C30(H30), C42(H42), C44(H44),
  C46(H46), C52(H52), C54(H54), C56(H56), C62(H62), C64(H64), C66(H66),
 C72(H72), C74(H74), C76(H76)
6.e Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C)
;
_shelx_res_checksum              6305
_shelx_hkl_checksum              12490
_olex2_submission_special_instructions 'No special instructions were received'