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_1575655
_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 H77 N4 P2, Cl'
_chemical_formula_sum            'C57 H77 Cl N4 P2'
_chemical_formula_weight         915.61
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-02
_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                 112.034(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6986(3)
_cell_length_b                   24.4943(4)
_cell_length_c                   16.1351(3)
_cell_measurement_reflns_used    10543
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      73.8730
_cell_measurement_theta_min      3.5280
_cell_volume                     5751.2(2)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.967
_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      5.00  83.00   0.50    1.59    --    0.00  19.00  30.00  156
  2  \w    -48.00   7.00   0.50    1.59    --    0.00 -38.00-120.00  110
  3  \w    -30.00  17.00   0.50    1.59    --    0.00 -57.00 150.00   94
  4  \w      6.00  36.00   0.50    6.35    --   95.20 -61.00-120.00   60
  5  \w     75.00 112.00   0.50    6.35    --   95.20 -30.00-120.00   74
  6  \w     23.00  59.00   0.50    6.35    --   95.20 -30.00-120.00   72
  7  \w     77.00 181.00   0.50    6.35    --   95.20  15.00   0.00  208
  8  \w     90.00 123.00   0.50    6.35    --   95.20 -82.00 -60.00   66
  9  \w      6.00  37.00   0.50    6.35    --   95.20 -82.00-120.00   62
 10  \w     42.00 127.00   0.50    6.35    --   95.20 -82.00-120.00  170
 11  \w      6.00  37.00   0.50    6.35    --   95.20 -61.00 -60.00   62
 12  \w     78.00 115.00   0.50    6.35    --   95.20 -61.00 -60.00   74
 13  \w     49.00 110.00   0.50    6.35    --   95.20 -61.00-120.00  122
 14  \w    159.00 184.00   0.50    6.35    --   95.20  15.00  60.00   50
 15  \w     77.00 131.00   0.50    6.35    --   95.20  15.00  60.00  108
;
_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      0.0362503000
_diffrn_orient_matrix_UB_12      0.0413902000
_diffrn_orient_matrix_UB_13      0.0773094000
_diffrn_orient_matrix_UB_21      0.0096975000
_diffrn_orient_matrix_UB_22      -0.0461478000
_diffrn_orient_matrix_UB_23      0.0677968000
_diffrn_orient_matrix_UB_31      0.0989708000
_diffrn_orient_matrix_UB_32      -0.0106415000
_diffrn_orient_matrix_UB_33      0.0063898000
_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  0.0255
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15552
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.025
_diffrn_reflns_theta_min         3.533
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.382
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72087
_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            'clear orangish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.057
_exptl_crystal_description       block
_exptl_crystal_F_000             1976
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         1.218
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         5660
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0484
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0473P)^2^+10.3747P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1140
_refine_ls_wR_factor_ref         0.1164
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5161
_reflns_number_total             5660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06158j2.cif
_cod_data_source_block           3a
_cod_depositor_comments
'Adding full bibliography for 1575654--1575657.cif.'
_cod_original_cell_volume        5751.21(19)
_cod_database_code               1575655
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.863
_shelx_estimated_absorpt_t_min   0.799
_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
 C1, P2, C3, P1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim P2 \\sim C3 \\sim P1: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(P1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(P1) = Uanis(C3)
4. Others
 Fixed Sof: C3(0.5) H3(0.5) P1(0.5)
5.a Riding coordinates:
 C3(H3)
5.b Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C25(H25), C28(H28)
5.c Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
5.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22)
5.e Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,
 H17C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,
 H29B,H29C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.303
_oxdiff_exptl_absorpt_empirical_full_min 0.681