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_1575656
_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'
_chemical_formula_sum            'C57 H77 N4 P2'
_chemical_formula_weight         880.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-07
_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                 102.619(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5434(14)
_cell_length_b                   12.8430(11)
_cell_length_c                   25.526(2)
_cell_measurement_reflns_used    9804
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      69.9560
_cell_measurement_theta_min      3.9690
_cell_volume                     5292.4(8)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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_temperature      150.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0671
_diffrn_reflns_av_unetI/netI     0.0625
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            42983
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.265
_diffrn_reflns_theta_min         1.635
_diffrn_source_current           3.57
_diffrn_source_power             0.24954300000000001
_diffrn_source_voltage           69.9
_exptl_absorpt_coefficient_mu    0.121
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.6399
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1410 before and 0.0855 after correction.
The Ratio of minimum to maximum transmission is 0.8514.
The \l/2 correction factor is Not present.
;
_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    1.105
_exptl_crystal_description       block
_exptl_crystal_F_000             1908
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.252
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.119
_refine_ls_abs_structure_details
;
 Flack x determined using 3714 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -1.07(8)
_refine_ls_extinction_coef       0.020(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         11473
_refine_ls_number_restraints     47
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.1132
_refine_ls_R_factor_gt           0.0992
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1721P)^2^+12.9261P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2766
_refine_ls_wR_factor_ref         0.2879
_reflns_Friedel_coverage         0.959
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                9461
_reflns_number_total             11473
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06158j2.cif
_cod_data_source_block           4a
_cod_depositor_comments
'Adding full bibliography for 1575654--1575657.cif.'
_cod_original_cell_volume        5292.5(8)
_cod_database_code               1575656
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.982
_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
 C5-P1 = C5A-P1A
 1.72 with sigma of 0.002
 C5A-C1
 1.48 with sigma of 0.02
 C5-C3
 1.48 with sigma of 0.02
 C29-C30 \\sim C29A-C30
 with sigma of 0.02
 C30-C31 \\sim C30-C31A
 with sigma of 0.02
 C44-C43 \\sim C44-C43A
 with sigma of 0.02
 C53-C54 \\sim C53-C54A
 with sigma of 0.02
 C53-C52 \\sim C53-C52A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C31A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C54A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(P1) = Uanis(C5A) = Uanis(P1A) = Uanis(C5)
4. Others
 Sof(C5A)=Sof(H5A)=Sof(P1A)=1-FVAR(1)
 Sof(C5)=Sof(H5)=Sof(P1)=FVAR(1)
 Sof(H30A)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=1-FVAR(2)
 Sof(H30)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(2)
 Sof(C31A)=Sof(H31D)=Sof(H31E)=Sof(H31F)=1-FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=FVAR(3)
 Sof(C43A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=1-FVAR(4)
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=FVAR(4)
 Sof(H53A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C54A)=Sof(H54D)=
 Sof(H54E)=Sof(H54F)=1-FVAR(5)
 Sof(H53)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C27(H27), C30(H30), C30(H30A), C41(H41), C44(H44),
 C53(H53), C53(H53A), C56(H56)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C32(H32A,H32B), C33(H33A,H33B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C22(H22), C23(H23), C24(H24), C36(H36),
 C38(H38), C37(H37), C50(H50), C48(H48), C49(H49), C5(H5), C5A(H5A)
5.d Fitted hexagon refined as free rotating group:
 C13(C12,C11,C10,C9,C8), C20(C21,C22,C23,C24,C25), C36(C35,C34,C39,C38,C37),
 C50(C51,C46,C47,C48,C49)
5.e Idealised Me refined as rotating group:
 C01E(H01A,H01B,H01C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C19(H19A,H19B,H19C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C40(H40A,
 H40B,H40C), C42(H42A,H42B,H42C), C45(H45A,H45B,H45C), C55(H55A,H55B,H55C),
 C29(H29A,H29B,H29C), C31(H31A,H31B,H31C), C43(H43A,H43B,H43C), C52(H52A,H52B,
 H52C), C54(H54A,H54B,H54C), C29A(H29D,H29E,H29F), C31A(H31D,H31E,H31F),
 C43A(H43D,H43E,H43F), C52A(H52D,H52E,H52F), C54A(H54D,H54E,H54F)
;
_olex2_submission_special_instructions 'No special instructions were received'