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_1575654
_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 H78 Cl N4 P2, Cl'
_chemical_formula_sum            'C57 H78 Cl2 N4 P2'
_chemical_formula_weight         952.07
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-07
_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                 118.148(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.5025(4)
_cell_length_b                   23.9957(2)
_cell_length_c                   25.7921(4)
_cell_measurement_reflns_used    22209
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.8310
_cell_measurement_theta_min      2.6880
_cell_volume                     13916.8(4)
_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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.966
_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     10.00  36.00   0.50    1.90    --    0.00  38.00 -90.00   52
  2  \w     -9.00  20.00   0.50    1.90    --    0.00 -57.00-180.00   58
  3  \w     26.00  58.00   0.50    1.90    --    0.00  77.00  30.00   64
  4  \w    -25.00   0.00   0.50    1.90    --    0.00  77.00  30.00   50
  5  \w    -83.00   3.00   0.50    1.90    --    0.00 -38.00  30.00  172
  6  \w    -54.00 -19.00   0.50    1.90    --    0.00 -57.00-180.00   70
  7  \w     38.00  99.00   0.50    4.00    --   95.20 -82.00 120.00  122
  8  \w     76.00 171.00   0.50    4.00    --   95.20  45.00-120.00  190
  9  \w     79.00 105.00   0.50    4.00    --   95.20 -82.00 -60.00   52
 10  \w     38.00  64.00   0.50    4.00    --   95.20 -82.00   0.00   52
 11  \w     92.00 117.00   0.50    4.00    --   95.20 -82.00   0.00   50
 12  \w     87.00 142.00   0.50    4.00    --   95.20  30.00 -60.00  110
 13  \w     50.00 127.00   0.50    4.00    --   95.20 -82.00-150.00  154
 14  \w     11.00  37.00   0.50    4.00    --   95.20 -82.00-150.00   52
 15  \w      6.00  98.00   0.50    4.00    --   95.20 -61.00 120.00  184
 16  \w     17.00  65.00   0.50    4.00    --   95.20 -82.00 -60.00   96
 17  \w     77.00 163.00   0.50    4.00    --   95.20  45.00-150.00  172
;
_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      0.0089477000
_diffrn_orient_matrix_UB_12      0.0625128000
_diffrn_orient_matrix_UB_13      -0.0069307000
_diffrn_orient_matrix_UB_21      -0.0376582000
_diffrn_orient_matrix_UB_22      0.0145728000
_diffrn_orient_matrix_UB_23      0.0305041000
_diffrn_orient_matrix_UB_31      0.0565026000
_diffrn_orient_matrix_UB_32      -0.0002132000
_diffrn_orient_matrix_UB_33      0.0600650000
_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  0.0284
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            42843
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.150
_diffrn_reflns_theta_min         2.693
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.501
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61829
_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 reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    0.909
_exptl_crystal_description       block
_exptl_crystal_F_000             4096
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.841
_refine_diff_density_min         -0.418
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     632
_refine_ls_number_reflns         13653
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0673
_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^)+(0.1405P)^2^+14.0027P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2229
_refine_ls_wR_factor_ref         0.2286
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11514
_reflns_number_total             13653
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06158j2.cif
_cod_data_source_block           2a
_cod_depositor_comments
'Adding full bibliography for 1575654--1575657.cif.'
_cod_database_code               1575654
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.852
_shelx_estimated_absorpt_t_min   0.795
_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
 C15-C17 \\sim C15-C17A
 with sigma of 0.02
 C17-C16 \\sim C17A-C16A
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C16-C18 \\sim C16A-C18A
 with sigma of 0.04
 C15-C16 \\sim C15-C16A
 with sigma of 0.04
 C15-C18 \\sim C15-C18A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
4. Others
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17A)=Sof(C18A)=
 Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C21(H21), C29(H29), C32(H32), C41(H41), C44(H44), C53(H53), C56(H56),
 C17(H17), C17A(H17A)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C24(H24), C25(H25), C26(H26), C36(H36),
 C37(H37), C38(H38), C48(H48), C49(H49), C50(H50)
5.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), 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), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C), C16A(H16D,H16E,H16F), C18A(H18D,H18E,H18F)
;
_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 1.465
_oxdiff_exptl_absorpt_empirical_full_min 0.545