Isomeric decker metallo-supramolecules with tunable luminescence and chiroptical properties.
Han, Ningxu; Ma, Jianjun; Yu, Hao; Shi, Junjuan; Dai, Manman; Guo, Ziteng; Gao, Zinuo; Zhang, Houyu; Wang, Ming; Chemical science 16 (2025) 21010–21019; doi:10.1039/d5sc04596g

data_1575939
_publ_section_title
;
 Isomeric decker metallo-supramolecules with tunable luminescence and
 chiroptical properties.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              21010
_journal_page_last               21019
_journal_paper_doi               10.1039/d5sc04596g
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C128 H103 B F2 N14 O2 Zn2, 3.5(F6 P)'
_chemical_formula_sum            'C128 H103 B F23 N14 O2 P3.5 Zn2'
_chemical_formula_weight         2556.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-04-03 deposited with the CCDC.	2025-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.658(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.9352(16)
_cell_length_b                   46.623(6)
_cell_length_c                   22.935(3)
_cell_measurement_reflns_used    9154
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      24.069
_cell_measurement_theta_min      2.194
_cell_volume                     14539(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.949
_diffrn_measured_fraction_theta_max 0.949
_diffrn_measurement_device_type  Synchrotron
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.68883
_diffrn_reflns_av_R_equivalents  0.0486
_diffrn_reflns_av_unetI/netI     0.0557
_diffrn_reflns_Laue_measured_fraction_full 0.949
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       55
_diffrn_reflns_limit_k_min       -55
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            163239
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        24.201
_diffrn_reflns_theta_max         24.201
_diffrn_reflns_theta_min         0.978
_diffrn_source_current           0.0
_diffrn_source_power             0.0
_diffrn_source_voltage           0.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.413
_exptl_absorpt_correction_T_max  0.7450
_exptl_absorpt_correction_T_min  0.6536
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1403 before and 0.0746 after correction.
The Ratio of minimum to maximum transmission is 0.8773.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.168
_exptl_crystal_description       block
_exptl_crystal_F_000             5238
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.003
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.114(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3151
_refine_ls_number_reflns         48584
_refine_ls_number_restraints     17427
_refine_ls_restrained_S_all      0.961
_refine_ls_R_factor_all          0.0674
_refine_ls_R_factor_gt           0.0599
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1185P)^2^+2.1408P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1636
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.967
_reflns_Friedel_fraction_full    0.943
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                42350
_reflns_number_total             48584
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04596g2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 1575939.cif.'
_cod_original_cell_volume        14538(3)
_cod_original_formula_sum        'C128 H103 B F23 N14 O2 P3.50 Zn2'
_cod_database_code               1575939
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.922
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.88578
 0.11422
2. Restrained distances
 P6-F34 = P6-F36 = P6-F38 = P6-F40 = P6-F42 = P6-F44
 1.65 with sigma of 0.02
 P7-F46 = P7-F23 = P7-F3 = P7-F25 = P7-F13 = P7-F27
 1.65 with sigma of 0.02
 P5-F17 = P5-F35 = P5-F9 = P5-F37 = P5-F19 = P5-F39
 1.65 with sigma of 0.02
 P2-F7 = P2-F29 = P2-F15 = P2-F31 = P2-F2 = P2-F33
 1.65 with sigma of 0.02
 P3-F5 = P3-F41 = P3-F21 = P3-F43 = P3-F11 = P3-F45
 1.65 with sigma of 0.02
 F17-F35 \\sim F17-F37 \\sim F17-F19 \\sim F17-F39 \\sim F9-F35 \\sim F9-F37
\\sim F9-F19 \\sim F9-F39
 with sigma of 0.04
 F34-F36 \\sim F34-F40 \\sim F34-F42 \\sim F34-F44 \\sim F38-F36 \\sim F38-F40
\\sim F38-F42 \\sim F38-F44
 with sigma of 0.04
 P5-F17 \\sim P5-F35 \\sim P5-F9 \\sim P5-F37 \\sim P5-F19 \\sim P5-F39
 with sigma of 0.02
 F34-F38 \\sim F36-F40 \\sim F44-F42
 with sigma of 0.05
 F17-F9 \\sim F35-F37 \\sim F39-F19
 with sigma of 0.05
 P7-F46 \\sim P7-F23 \\sim P7-F3 \\sim P7-F25 \\sim P7-F13 \\sim P7-F27
 with sigma of 0.02
 P6-F34 \\sim P6-F36 \\sim P6-F38 \\sim P6-F40 \\sim P6-F42 \\sim P6-F44
 with sigma of 0.02
 F46-F23 \\sim F46-F25 \\sim F46-F13 \\sim F46-F27 \\sim F3-F23 \\sim F3-F25
\\sim F3-F13 \\sim F3-F27
 with sigma of 0.04
 F46-F3 \\sim F23-F25 \\sim F27-F13
 with sigma of 0.05
 P2-F7 \\sim P2-F29 \\sim P2-F15 \\sim P2-F31 \\sim P2-F2 \\sim P2-F33
 with sigma of 0.02
 F7-F29 \\sim F7-F31 \\sim F7-F2 \\sim F7-F33 \\sim F15-F29 \\sim F15-F31 \\sim
F15-F2 \\sim F15-F33
 with sigma of 0.04
 F7-F15 \\sim F29-F31 \\sim F33-F2
 with sigma of 0.05
 P3-F5 \\sim P3-F41 \\sim P3-F21 \\sim P3-F43 \\sim P3-F11 \\sim P3-F45
 with sigma of 0.02
 F5-F21 \\sim F41-F43 \\sim F45-F11
 with sigma of 0.05
 F5-F41 \\sim F5-F43 \\sim F5-F11 \\sim F5-F45 \\sim F21-F41 \\sim F21-F43
\\sim F21-F11 \\sim F21-F45
 with sigma of 0.04
3. Rigid bond restraints
 C119, C2, C111, C115
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F42, P6, F36, F44, F38, F40, F34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C1 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C9 \\sim C10 \\sim C13 \\sim C14
\\sim C15 \\sim C19 \\sim C20 \\sim C21 \\sim C27 \\sim C28 \\sim C29 \\sim C32
\\sim C33 \\sim C34 \\sim C35 \\sim C37 \\sim C40 \\sim C41 \\sim C45 \\sim C49
\\sim C50 \\sim C51 \\sim C55 \\sim C56 \\sim C59 \\sim C60 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C75 \\sim C77 \\sim C80 \\sim C82 \\sim C83 \\sim C84 \\sim C86 \\sim C87
\\sim C89 \\sim C90 \\sim C91 \\sim C93 \\sim C96 \\sim C98 \\sim C99 \\sim
C100 \\sim C101 \\sim C104 \\sim C107 \\sim C109 \\sim C110 \\sim C112 \\sim
C113 \\sim C114 \\sim C116 \\sim C117 \\sim C120 \\sim C121 \\sim C122 \\sim
C124 \\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim
C138 \\sim C142 \\sim C144 \\sim C148 \\sim C149 \\sim C150 \\sim C154 \\sim
C156 \\sim C157 \\sim C159 \\sim C163 \\sim C164 \\sim C166 \\sim C167 \\sim
C169 \\sim C171 \\sim C175 \\sim C177 \\sim C182 \\sim C183 \\sim C186 \\sim
C190 \\sim C193 \\sim C196 \\sim C197 \\sim C199 \\sim C201 \\sim C202 \\sim
C203 \\sim C205 \\sim C209 \\sim C210 \\sim C211 \\sim C214 \\sim C216 \\sim
C221 \\sim C226 \\sim C227 \\sim C229 \\sim C232 \\sim C234 \\sim C235 \\sim
C238 \\sim C239 \\sim C241 \\sim C242 \\sim C243 \\sim C246 \\sim C252 \\sim
C256 \\sim C257 \\sim C2 \\sim C3 \\sim C8 \\sim C11 \\sim C12 \\sim C16 \\sim
C17 \\sim C18 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C30 \\sim
C31 \\sim C36 \\sim C38 \\sim C39 \\sim C42 \\sim C43 \\sim C44 \\sim C46 \\sim
C47 \\sim C48 \\sim C52 \\sim C53 \\sim C54 \\sim C57 \\sim C58 \\sim C61 \\sim
C62 \\sim C63 \\sim C74 \\sim C76 \\sim C78 \\sim C79 \\sim C81 \\sim C85 \\sim
C88 \\sim C94 \\sim C95 \\sim C97 \\sim C102 \\sim C103 \\sim C105 \\sim C106
\\sim C108 \\sim C111 \\sim C115 \\sim C118 \\sim C119 \\sim C123 \\sim C125
\\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C139
\\sim C140 \\sim C141 \\sim C143 \\sim C145 \\sim C146 \\sim C147 \\sim C151
\\sim C152 \\sim C153 \\sim C155 \\sim C158 \\sim C160 \\sim C162 \\sim C165
\\sim C168 \\sim C170 \\sim C172 \\sim C173 \\sim C174 \\sim C176 \\sim C178
\\sim C179 \\sim C180 \\sim C181 \\sim C184 \\sim C185 \\sim C187 \\sim C188
\\sim C189 \\sim C191 \\sim C192 \\sim C194 \\sim C195 \\sim C198 \\sim C200
\\sim C204 \\sim C206 \\sim C207 \\sim C208 \\sim C212 \\sim C213 \\sim C215
\\sim C217 \\sim C218 \\sim C219 \\sim C220 \\sim C222 \\sim C223 \\sim C224
\\sim C225 \\sim C228 \\sim C230 \\sim C231 \\sim C233 \\sim C236 \\sim C237
\\sim C240 \\sim C244 \\sim C245 \\sim C247 \\sim C248 \\sim C249 \\sim C250
\\sim C251 \\sim C253 \\sim C254 \\sim C255 \\sim C258 \\sim N1 \\sim N6 \\sim
N7 \\sim N8 \\sim N10 \\sim N12 \\sim N16 \\sim N17 \\sim N20 \\sim N21 \\sim
N23 \\sim N24 \\sim N26 \\sim N161 \\sim N2 \\sim N3 \\sim N4 \\sim N5 \\sim N9
\\sim N11 \\sim N13 \\sim N14 \\sim N15 \\sim N18 \\sim N19 \\sim N22 \\sim N25
\\sim N27: within 5A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 5A
O2 \\sim O3 \\sim O1 \\sim O4: within 5A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 5A
P2 \\sim F2 \\sim F7 \\sim F15 \\sim F29 \\sim F31 \\sim F33: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
P6 \\sim F34 \\sim F36 \\sim F38 \\sim F40 \\sim F42 \\sim F44: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
P7 \\sim F3 \\sim F13 \\sim F23 \\sim F25 \\sim F27 \\sim F46: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
P5 \\sim F9 \\sim F17 \\sim F19 \\sim F35 \\sim F37 \\sim F39: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
P3 \\sim F5 \\sim F11 \\sim F21 \\sim F41 \\sim F43 \\sim F45: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 P2, F2, F7, F15, F29, F31, F33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P6, F34, F36, F38, F40, F42, F44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P7, F3, F13, F23, F25, F27, F46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P5, F9, F17, F19, F35, F37, F39
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P3, F5, F11, F21, F41, F43, F45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C9(H9), C13(H13), C14(H14), C15(H15), C27(H27), C28(H28),
 C32(H32), C33(H33), C34(H34), C49(H49), C50(H50), C55(H55), C60(H60), C65(H65),
  C66(H66), C67(H67), C68(H68), C70(H70), C71(H71), C72(H72), C73(H73),
 C75(H75), C82(H82), C83(H83), C86(H86), C87(H87), C89(H89), C107(H107),
 C109(H109), C110(H110), C114(H114), C116(H116), C120(H120), C121(H121),
 C132(H132), C133(H133), C138(H138), C148(H148), C149(H149), C154(H154),
 C157(H157), C159(H159), C163(H163), C171(H171), C175(H175), C183(H183),
 C190(H190), C196(H196), C199(H199), C201(H201), C205(H205), C209(H209),
 C210(H210), C221(H221), C226(H226), C227(H227), C238(H238), C241(H241),
 C243(H243), C246(H246), C256(H256), C257(H257), C8(H8), C11(H11), C16(H16),
 C22(H22), C23(H23), C25(H25), C42(H42), C43(H43), C44(H44), C47(H47), C53(H53),
  C54(H54), C57(H57), C58(H58), C63(H63), C74(H74), C78(H78), C79(H79),
 C85(H85), C95(H95), C103(H103), C105(H105), C106(H106), C108(H108), C118(H118),
  C125(H125), C127(H127), C129(H129), C131(H131), C143(H143), C146(H146),
 C153(H153), C155(H155), C158(H158), C160(H160), C165(H165), C168(H168),
 C170(H170), C173(H173), C176(H176), C179(H179), C181(H181), C188(H188),
 C191(H191), C192(H192), C206(H206), C215(H215), C219(H219), C220(H220),
 C223(H223), C224(H224), C225(H225), C228(H228), C233(H233), C237(H237),
 C240(H240), C244(H244), C247(H247), C249(H249), C251(H251), C253(H253),
 C254(H254), C255(H255), C258(H258)
6.b Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C51(H51A,H51B,H51C), C77(H77A,H77B,H77C), C104(H10A,H10B,
 H10C), C113(H11A,H11B,H11C), C117(H11D,H11E,H11F), C156(H15A,H15B,H15C),
 C193(H19A,H19B,H19C), C197(H19D,H19E,H19F), C203(H20A,H20B,H20C), C216(H21A,
 H21B,H21C), C232(H23A,H23B,H23C), C235(H23D,H23E,H23F), C2(H2A,H2B,H2C),
 C52(H52A,H52B,H52C), C88(H88A,H88B,H88C), C111(H11G,H11H,H11I), C115(H11J,H11K,
 H11L), C147(H14A,H14B,H14C), C151(H15D,H15E,H15F), C162(H16A,H16B,H16C),
 C187(H18A,H18B,H18C), C189(H18D,H18E,H18F), C207(H20D,H20E,H20F), C213(H21D,
 H21E,H21F), C248(H24A,H24B,H24C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              84981
_shelx_fab_checksum              25133
_olex2_submission_special_instructions 'No special instructions were received'