Büchner-type ring expansion of aromatic main-group biradicaloids toward phosphorus radical-derived NIR-II photothermal materials.
Liu, Shihua; Zheng, Shunlin; Lin, Jieli; Grützmacher, Hansjörg; Su, Cheng-Yong; Li, Zhongshu; Chemical science 16 (2025) 18775–18782; doi:10.1039/d5sc06158j

data_1575657
_publ_section_title
;
 B&#xfc;chner-type ring expansion of aromatic main-group biradicaloids
 toward phosphorus radical-derived NIR-II photothermal materials.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              18775
_journal_page_last               18782
_journal_paper_doi               10.1039/d5sc06158j
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C57 H74 Cl N4 P2, Cl, 4(C6 H5 F)'
_chemical_formula_sum            'C81 H94 Cl2 F4 N4 P2'
_chemical_formula_weight         1332.44
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-14 deposited with the CCDC.	2025-09-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.9060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.01290(10)
_cell_length_b                   24.51340(10)
_cell_length_c                   24.10330(10)
_cell_measurement_reflns_used    45893
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.9020
_cell_measurement_theta_min      2.5990
_cell_volume                     7494.49(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     30.00  65.00   0.50    2.00    --    0.00  38.00 -90.00   70
  2  \w     -9.00  22.00   0.50    2.00    --    0.00  38.00 -90.00   62
  3  \w    -29.00  11.00   0.50    2.00    --    0.00 -57.00-120.00   80
  4  \w    -89.00  17.00   0.50    2.00    --    0.00 -19.00   0.00  212
  5  \w     31.00  77.00   0.50    2.00    --    0.00  57.00  90.00   92
  6  \w    -87.00  17.00   0.50    2.00    --    0.00 -38.00 120.00  208
  7  \w    103.00 129.00   0.50    8.00    --   95.20  30.00 120.00   52
  8  \w     17.00 126.00   0.50    8.00    --   95.20 -82.00-180.00  218
  9  \w     32.00  73.00   0.50    8.00    --   95.20 -45.00 -60.00   82
 10  \w     80.00 185.00   0.50    8.00    --   95.20  30.00  30.00  210
 11  \w     78.00 103.00   0.50    8.00    --   95.20 -82.00 120.00   50
 12  \w     66.00 126.00   0.50    8.00    --   95.20 -82.00 -90.00  120
 13  \w     79.00 171.00   0.50    8.00    --   95.20  30.00 -60.00  184
 14  \w     35.00 119.00   0.50    8.00    --   95.20 -82.00  60.00  168
 15  \w     87.00 123.00   0.50    8.00    --   95.20 -82.00-120.00   72
 16  \w    135.00 174.00   0.50    8.00    --   95.20  30.00  60.00   78
 17  \w     15.00  40.00   0.50    8.00    --   95.20 -82.00-120.00   50
 18  \w     71.00 104.00   0.50    8.00    --   95.20 -61.00  60.00   66
 19  \w     14.00 116.00   0.50    8.00    --   95.20 -61.00-180.00  204
 20  \w     81.00 173.00   0.50    8.00    --   95.20  30.00 -30.00  184
 21  \w     27.00  64.00   0.50    8.00    --   95.20 -61.00  60.00   74
 22  \w     94.00 120.00   0.50    8.00    --   95.20 -82.00  30.00   52
 23  \w     43.00 126.00   0.50    8.00    --   95.20 -82.00 -30.00  166
 24  \w     80.00 129.00   0.50    8.00    --   95.20  30.00  60.00   98
 25  \w     78.00 103.00   0.50    8.00    --   95.20 -82.00 129.47   50
 26  \w     77.00 102.00   0.50    8.00    --   95.20 -82.00 150.00   50
 27  \w     10.00  59.00   0.50    8.00    --   95.20 -82.00 129.47   98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0556030000
_diffrn_orient_matrix_UB_12      0.0121713000
_diffrn_orient_matrix_UB_13      -0.0487593000
_diffrn_orient_matrix_UB_21      0.0340274000
_diffrn_orient_matrix_UB_22      0.0562379000
_diffrn_orient_matrix_UB_23      0.0263301000
_diffrn_orient_matrix_UB_31      0.1024332000
_diffrn_orient_matrix_UB_32      -0.0253009000
_diffrn_orient_matrix_UB_33      0.0350661000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0232
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            86312
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.253
_diffrn_reflns_theta_min         2.605
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.615
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63442
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic reddish red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       block
_exptl_crystal_F_000             2832
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.366
_refine_diff_density_min         -1.139
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     826
_refine_ls_number_reflns         15053
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.164
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0898P)^2^+5.5450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1605
_refine_ls_wR_factor_ref         0.1642
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13543
_reflns_number_total             15053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06158j2.cif
_cod_data_source_block           2b
_cod_depositor_comments
'Adding full bibliography for 1575654--1575657.cif.'
_cod_database_code               1575657
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.855
_shelx_estimated_absorpt_t_min   0.794
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 F2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(F2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
4. Others
 Fixed Sof: F3(0.5) C69(0.5) C70(0.5) H70(0.5) C71(0.5) H71(0.5) C72(0.5)
 H72(0.5) C73(0.5) H73(0.5) C74(0.5) H74(0.5) H76(0.6) H79(0.4) F4(0.4) F5(0.6)
 F6(0.5) C81(0.5) H81(0.5) C82(0.5) C83(0.5) H83(0.5) C84(0.5) H84(0.5)
 C85(0.5) H85(0.5) C86(0.5) H86(0.5)
5.a Free rotating group:
 F3(C69,C70,C71,C72,C73,C74), F6(C81,C82,C83,C84,C85,C86)
5.b Ternary CH refined with riding coordinates:
 C17(H17), C20(H20), C29(H29), C32(H32), C41(H41), C44(H44), C53(H53), C56(H56)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
5.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14), C24(H24),
 C25(H25), C26(H26), C36(H36), C37(H37), C38(H38), C48(H48), C49(H49), C50(H50),
  C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76),
 C77(H77), C78(H78), C79(H79), C80(H80), C024(H024), C65(H65), C66(H66),
 C67(H67), C68(H68), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C81(H81),
  C83(H83), C84(H84), C85(H85), C86(H86)
5.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,
 H33B,H33C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C),
 C45(H45A,H45B,H45C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C57(H57A,H57B,H57C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.492
_oxdiff_exptl_absorpt_empirical_full_min 0.712