Deconvoluting capping ligand influence on photophysical properties in tetrathiafulvalene-based diradicaloids.
Lopez, Nathan E.; McNamara, Lauren E.; Anferov, Sophie W.; Anderson, John S.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 908–914; doi:10.1039/d4dt03305a

data_7717735
_publ_section_title
;
 Deconvoluting capping ligand influence on photophysical properties in
 tetrathiafulvalene-based diradicaloids.
;
_journal_issue                   3
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              908
_journal_page_last               914
_journal_paper_doi               10.1039/d4dt03305a
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C45 H24 F18 O6 P2 Pt S4, C32 H11 B F24'
_chemical_formula_sum            'C77 H35 B F42 O6 P2 Pt S4'
_chemical_formula_weight         2250.13
_chemical_name_common            '[((P(O(4-CF3-Ph)3)2)Pt)2Ttftt](BArF4)2'
_chemical_name_systematic
'(\m-2-[4,5-bis(sulfanyl)-2H-1,3-dithiol-2-ylidene]-2H-1,3-dithiole-4,5-dithiolato diradical dication)-bis[(para-trifluoromethylphenylphosphite)]-di-platinum(ii) bis(tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-08-13 deposited with the CCDC.	2024-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                77.831(8)
_cell_angle_beta                 78.221(8)
_cell_angle_gamma                79.506(9)
_cell_formula_units_Z            2
_cell_length_a                   14.630(4)
_cell_length_b                   15.470(4)
_cell_length_c                   19.500(5)
_cell_measurement_reflns_used    3906
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.21
_cell_measurement_theta_min      2.17
_cell_volume                     4178.5(19)
_computing_cell_refinement       'SAINT V.8.40B (Bruker AXS LLC., 2019)'
_computing_data_collection       'APEX4 v.2022.10-0 (Bruker AXS LLC., 2022)'
_computing_data_reduction        'SAINT V.8.40B (Bruker AXS LLC., 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL-2019/3 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON II'
_diffrn_detector_area_resol_mean 7.4
_diffrn_detector_type
;
Charge-Integrating Pixel Array Detector (CPADs)
;
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1299
_diffrn_reflns_av_unetI/netI     0.1042
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            64722
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        23.403
_diffrn_reflns_theta_max         23.403
_diffrn_reflns_theta_min         1.830
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.963
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1111 before and 0.0888 after correction.
 The Ratio of minimum to maximum transmission is 0.68.

Final HKLF 4 output contains 18803 reflections, Rint = 0.1158
 (6770 with I > 3sig(I), Rint = 0.0837)
;
_exptl_crystal_colour            'clear orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.788
_exptl_crystal_description       prism
_exptl_crystal_F_000             2200
_exptl_crystal_size_max          0.243
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.073
_refine_diff_density_max         6.174
_refine_diff_density_min         -2.338
_refine_diff_density_rms         0.367
_refine_ls_extinction_coef       0.0081(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         12109
_refine_ls_number_restraints     3567
_refine_ls_restrained_S_all      0.943
_refine_ls_R_factor_all          0.2834
_refine_ls_R_factor_gt           0.2214
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0999P)^2^+870.0123P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.5152
_refine_ls_wR_factor_ref         0.5530
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7903
_reflns_number_total             12109
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03305a2.cif
_cod_data_source_block           1868_nelanderson2
_cod_depositor_comments
'Adding full bibliography for 7717733--7717738.cif.'
_cod_database_code               7717735
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.870
_shelx_estimated_absorpt_t_min   0.647
_olex2_refinement_description
;
1. Restrained distances
 C19-C18 \\sim C24-C18 \\sim C23-C24 \\sim C23-C21 \\sim C20-C21 \\sim C20-C19
\\sim C5-C4 \\sim C6-C5 ~
 C7-C6 \\sim C9-C7 \\sim C9-C10 \\sim C10-C4 \\sim C12-C11 \\sim C13-C12 \\sim
C16-C14 \\sim C13-C14 \\sim C17-
 C16 \\sim C17-C11 \\sim C32-C38 \\sim C32-C33 \\sim C33-C34 \\sim C35-C34
\\sim C35-C37 \\sim C37-C38 ~
 C27-C26 \\sim C27-C28 \\sim C30-C28 \\sim C30-C31 \\sim C31-C25 \\sim C26-C25
\\sim C40-C39 \\sim C45-C39
 \\sim C44-C45 \\sim C44-C42 \\sim C41-C42 \\sim C41-C40 \\sim C46-C47 \\sim
C46-C53 \\sim C53-C51 \\sim C50-
 C51 \\sim C48-C50 \\sim C48-C47 \\sim C70-C77 \\sim C70-C71 \\sim C72-C71
\\sim C72-C74 \\sim C74-C75 ~
 C75-C77 \\sim C55-C56 \\sim C56-C58 \\sim C58-C59 \\sim C61-C59 \\sim C61-C54
\\sim C55-C54 \\sim C62-C63
 \\sim C69-C62 \\sim C69-C67 \\sim C66-C67 \\sim C66-C64 \\sim C64-C63
 with sigma of 0.01
 C60-C59 \\sim C56-C57 \\sim C7-C8 \\sim C73-C72 \\sim C76-C75 \\sim C15-C14
\\sim C29-C28 \\sim C35-C36 ~
 C43-C42 \\sim C22-C21 \\sim C52-C51 \\sim C49-C48 \\sim C68-C67 \\sim C65-C64
 with sigma of 0.01
 F25-C57 \\sim F26-C57 \\sim F27-C57 \\sim F30-C60 \\sim F28-C60 \\sim F29-C60
\\sim F23-C52 \\sim F22-C52
 \\sim F24-C52 \\sim F42-C76 \\sim F40-C76 \\sim F41-C76 \\sim F39-C73 \\sim
F38-C73 \\sim F37-C73 \\sim F31-
 C65 \\sim F33-C65 \\sim F32-C65 \\sim F35-C68 \\sim F34-C68 \\sim F3-C8 \\sim
F2-C8 \\sim F1-C8 \\sim F36-C68
 \\sim F20-C49 \\sim F19-C49 \\sim F21-C49 \\sim F14-C29 \\sim F15-C29 \\sim
F13-C29 \\sim F12-C36 \\sim F10-
 C36 \\sim F11-C36 \\sim F18-C43 \\sim F16-C43 \\sim F17-C43 \\sim F5-C15 \\sim
F6-C15 \\sim F4-C15 \\sim F9-
 C22 \\sim F8-C22 \\sim F7-C22
 with sigma of 0.01
 O3-C18 \\sim O1-C4 \\sim O2-C11 \\sim O5-C32 \\sim O6-C39 \\sim O4-C25
 with sigma of 0.01
 P1-O1 \\sim P1-O2 \\sim P1-O3 \\sim P2-O4 \\sim P2-O6 \\sim P2-O5
 with sigma of 0.01
 C54-B1 \\sim C62-B1 \\sim C46-B1 \\sim C70-B1
 with sigma of 0.01
 F5-F6 \\sim F6-F4
 with sigma of 0.02
 F4-F6 \\sim F4A-F6A
 with sigma of 0.02
 F6-C14 \\sim F6A-C14
 with sigma of 0.02
 F4-C14 \\sim F4A-C14
 with sigma of 0.04
 F4-C15 \\sim F4A-C15
 with sigma of 0.04
 F6-C15 \\sim F6A-C15
 with sigma of 0.04
 C15-F4A \\sim C15-F4B
 with sigma of 0.02
 F6A-F4A \\sim F6A-F4B
 with sigma of 0.02
 F38-C73 \\sim F38A-C73
 with sigma of 0.02
 F39-C73 \\sim F39A-C73
 with sigma of 0.02
 F14-C29 \\sim F14A-C29
 with sigma of 0.02
 F15-C29 \\sim F15A-C29
 with sigma of 0.02
 F29-C60 \\sim F29A-C60
 with sigma of 0.02
 F30-C60 \\sim F30A-C60
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
Uanis(C42) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(P1) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C55) \\sim Ueq,
Uanis(C58) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(S2)
\\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(F38) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(B1) \\sim Ueq,
Uanis(C41) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(F12) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(S4) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(O6) \\sim Ueq, Uanis(F32) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(F41)
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(F35) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C50) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C66) \\sim Ueq,
Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(F2) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(F9) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(C15) \\sim Ueq,
Uanis(F17) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O4)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F13) \\sim Ueq,
Uanis(F11) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(F10) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(F14) \\sim Ueq,
Uanis(C57) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(F33) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(F39) \\sim Ueq,
Uanis(F37) \\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(F42)
\\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(F26) \\sim Ueq, Uanis(F40) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F34)
\\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(F27) \\sim Ueq,
Uanis(C72) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F28) \\sim Ueq, Uanis(C67)
\\sim Ueq, Uanis(F29) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(F30) \\sim Ueq,
Uanis(F31) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(C76)
\\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(Pt1) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C70)
\\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(P2) \\sim Ueq, Uanis(C65) \\sim Ueq:
with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O4) = Uanis(O6) = Uanis(O5) = Uanis(O3) = Uanis(O2) = Uanis(O1)
Uanis(C32) = Uanis(C33) = Uanis(C34) = Uanis(C35) = Uanis(C37) = Uanis(C38) =
Uanis(C28) = Uanis(C25) = Uanis(C26) = Uanis(C27) = Uanis(C30) = Uanis(C31) =
Uanis(C2) = Uanis(C1) = Uanis(C3) = Uanis(C7) = Uanis(C6) = Uanis(C5) =
Uanis(C4) = Uanis(C10) = Uanis(C9) = Uanis(C42) = Uanis(C39) = Uanis(C40) =
Uanis(C41) = Uanis(C45) = Uanis(C44) = Uanis(C17) = Uanis(C16) = Uanis(C14) =
Uanis(C13) = Uanis(C12) = Uanis(C11) = Uanis(C62) = Uanis(C63) = Uanis(C66) =
Uanis(C69) = Uanis(C67) = Uanis(C64) = Uanis(C54) = Uanis(C56) = Uanis(C55) =
Uanis(C58) = Uanis(C59) = Uanis(C61) = Uanis(C51) = Uanis(C50) = Uanis(C48) =
Uanis(C47)
Uanis(C36) = Uanis(C57) = Uanis(C43) = Uanis(C29)
Uanis(F25) = Uanis(F27) = Uanis(F26) = Uanis(F11) = Uanis(F12) = Uanis(F10)
Uanis(F39A) = Uanis(F38) = Uanis(F38A) = Uanis(F39) = Uanis(F37) = Uanis(F30A)
= Uanis(F30) = Uanis(F29) = Uanis(F29A) = Uanis(F14A) = Uanis(F15A) =
Uanis(F15) = Uanis(F14) = Uanis(F13)
Uanis(F4B) = Uanis(F5) = Uanis(F6) = Uanis(F6A) = Uanis(F4) = Uanis(F4A) =
Uanis(F3) = Uanis(F1) = Uanis(F2)
3. Others
 Fixed Sof: F4(0.5) F5(0.5) F6(0.5) F14(0.5) F15(0.5) F29(0.5) F30(0.5)
 F38(0.5) F39(0.5) F6A(0.5) F4A(0.5) F4B(0.5) F39A(0.5) F38A(0.5) F14A(0.5)
 F15A(0.5) F29A(0.5) F30A(0.5)
4.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13), C16(H16), C17(H17),
 C19(H19), C20(H20), C23(H23), C24(H24), C26(H26), C27(H27), C30(H30), C31(H31),
  C33(H33), C34(H34), C37(H37), C38(H38), C40(H40), C41(H41), C44(H44),
 C45(H45), C47(H47), C50(H50), C53(H53), C55(H55), C58(H58), C61(H61), C63(H63),
  C66(H66), C69(H69), C74(H74), C77(H77)
;
_shelx_res_checksum              36693
_olex2_submission_special_instructions 'No special instructions were received'