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_7717738
_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
'0.5(C90 O12 P4 Pt2 S8), B C32 F24, 0.25[], 0.25[], 0.25[], 0.125[], 0.75[], 0.375[]'
_chemical_formula_sum            'C77 H54 B F24 O6 P2 Pt S4'
_chemical_formula_weight         1927.28
_chemical_name_common            '[((P(O(2-CH3-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[(ortho-methylphenylphosphite)]-di-platinum(ii) bis(tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)'
_chemical_properties_physical    Light-sensitive,Photo-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                90
_cell_angle_beta                 99.619(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   26.9879(15)
_cell_length_b                   21.3132(11)
_cell_length_c                   29.4717(16)
_cell_measurement_reflns_used    9685
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22.84
_cell_measurement_theta_min      2.31
_cell_volume                     16713.7(16)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.1068
_diffrn_reflns_av_unetI/netI     0.0633
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            388919
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.745
_diffrn_reflns_theta_max         24.745
_diffrn_reflns_theta_min         1.762
_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    1.920
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.6535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0941 before and 0.0777 after correction.
The Ratio of minimum to maximum transmission is 0.8773.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.532
_exptl_crystal_description       prism
_exptl_crystal_F_000             7656
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.075
_refine_diff_density_max         13.234
_refine_diff_density_min         -2.993
_refine_diff_density_rms         0.289
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.441
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1924
_refine_ls_number_reflns         28557
_refine_ls_number_restraints     3432
_refine_ls_restrained_S_all      1.399
_refine_ls_R_factor_all          0.2169
_refine_ls_R_factor_gt           0.1272
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3053
_refine_ls_wR_factor_ref         0.4029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15378
_reflns_number_total             28557
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03305a2.cif
_cod_data_source_block           1865_nel_anderson1
_cod_depositor_comments
'Adding full bibliography for 7717733--7717738.cif.'
_cod_database_code               7717738
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.869
_shelx_estimated_absorpt_t_min   0.794
_olex2_refinement_description
;
1. Restrained distances
 C83-C82 \\sim C62-C61 \\sim C55-C54 \\sim C68-C69 \\sim C75-C76 \\sim C27-C26
\\sim C13-C12 \\sim C19-C20
 \\sim C41-C40 \\sim C48-C47 \\sim C33-C34
 with sigma of 0.04
 C57-C56 \\sim C57-C58 \\sim C58-C59 \\sim C60-C59 \\sim C60-C61 \\sim C56-C61
\\sim C52-C53 \\sim C53-C54
 \\sim C54-C49 \\sim C50-C49 \\sim C51-C50 \\sim C51-C52 \\sim C71-C70 \\sim
C75-C70 \\sim C72-C71 \\sim C73-
 C72 \\sim C73-C74 \\sim C75-C74 \\sim C67-C68 \\sim C68-C63 \\sim C64-C63
\\sim C65-C64 \\sim C65-C66 ~
 C66-C67 \\sim C85-C86 \\sim C82-C77 \\sim C81-C82 \\sim C78-C77 \\sim C79-C78
\\sim C79-C80 \\sim C80-C81
 \\sim C28-C29 \\sim C28-C33 \\sim C32-C33 \\sim C31-C32 \\sim C31-C30 \\sim
C30-C29 \\sim C12-C7 \\sim C7-C8 ~
 C9-C8 \\sim C10-C9 \\sim C11-C10 \\sim C11-C12 \\sim C14-C15 \\sim C16-C15
\\sim C17-C16 \\sim C17-C18 ~
 C18-C19 \\sim C19-C14 \\sim C26-C21 \\sim C25-C26 \\sim C25-C24 \\sim C23-C24
\\sim C23-C22 \\sim C22-C21
 \\sim C40-C35 \\sim C36-C35 \\sim C37-C36 \\sim C38-C37 \\sim C38-C39 \\sim
C39-C40 \\sim C47-C42 \\sim C43-
 C42 \\sim C44-C43 \\sim C44-C45 \\sim C45-C46 \\sim C46-C47
 with sigma of 0.04
 O12-C84 \\sim O12-C84A
 with sigma of 0.04
 C89-C88 \\sim C89A-C88A
 with sigma of 0.02
 C89-C84 \\sim C89A-C84A
 with sigma of 0.02
 C88-C159 \\sim C88A-C87
 with sigma of 0.02
 C159-C86 \\sim C87-C86A
 with sigma of 0.02
 C86-C85 \\sim C86A-C85A
 with sigma of 0.02
 C85-C84 \\sim C85A-C84A
 with sigma of 0.02
 O12-C89 \\sim O12-C89A
 with sigma of 0.04
 O12-C85 \\sim O12-C85A
 with sigma of 0.04
 C89-C159 \\sim C89A-C87
 with sigma of 0.04
 C89-C85 \\sim C89A-C85A
 with sigma of 0.04
 C88-C86 \\sim C88A-C86A
 with sigma of 0.04
 C88-C84 \\sim C88A-C84A
 with sigma of 0.04
 C159-C85 \\sim C87-C85A
 with sigma of 0.04
 C86-C84 \\sim C86A-C84A
 with sigma of 0.04
 C85A-C155 \\sim C90-C89 \\sim C76-C75 \\sim C62-C61 \\sim C55-C54 \\sim
C20-C19 \\sim C27-C26 \\sim C41-
 C40 \\sim C48-C47 \\sim C34-C33 \\sim C13-C12 \\sim C69-C68 \\sim C83-C82
 with sigma of 0.04
 F34-C137 \\sim F34A-C137 \\sim F35-C137 \\sim F35A-C137 \\sim F36-C137 \\sim
F36A-C137 \\sim F31-C134
 \\sim F31A-C134 \\sim F32-C134 \\sim F32A-C134 \\sim F33-C134 \\sim F33A-C134
 with sigma of 0.04
2. Rigid bond restraints
 F15, F1, C94, F2, F3, C93, C92, C95, C91, C96, C98, B1, C97, C99, C107, C115,
 F4, F5, F6, C100, C106, C108, C114, C116, C122, C101, C104, C109, C112, C117,
 C120, C102, C103, C105, C110, C111, C113, C118, C119, C121, F7, F8, F9, F10,
 F11, F12, F13, F14, F16, F17, F18, F19, F20, F21, F22, F23, F24, F26, F25,
 C126, F27, C125, C124, C127, C123, C128, C130, B2, C129, C131, C139, C147, F28,
  F29, F30, C132, C138, C140, C146, C148, C154, C133, C136, C141, C144, C149,
 C152, C134, C135, C137, C142, C143, C145, C150, C151, C153, F31, F32, F33,
 F33A, F32A, F31A, F34, F35, F36, F35A, F36A, F34A, F37, F38, F39, F40, F41,
 F42, F43, F44, F45, F46, F47, F48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(F35) \\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(C126) \\sim Ueq, Uanis(F26)
\\sim Ueq, Uanis(F27) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C124) \\sim Ueq,
Uanis(C127) \\sim Ueq, Uanis(C123) \\sim Ueq, Uanis(C128) \\sim Ueq,
Uanis(C130) \\sim Ueq, Uanis(B2) \\sim Ueq, Uanis(C129) \\sim Ueq, Uanis(C131)
\\sim Ueq, Uanis(C139) \\sim Ueq, Uanis(C147) \\sim Ueq, Uanis(F28) \\sim Ueq,
Uanis(F29) \\sim Ueq, Uanis(F30) \\sim Ueq, Uanis(C132) \\sim Ueq, Uanis(C138)
\\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C146) \\sim Ueq, Uanis(C148) \\sim Ueq,
Uanis(C154) \\sim Ueq, Uanis(C133) \\sim Ueq, Uanis(C136) \\sim Ueq,
Uanis(C141) \\sim Ueq, Uanis(C144) \\sim Ueq, Uanis(C149) \\sim Ueq,
Uanis(C152) \\sim Ueq, Uanis(C134) \\sim Ueq, Uanis(C135) \\sim Ueq,
Uanis(C137) \\sim Ueq, Uanis(C142) \\sim Ueq, Uanis(C143) \\sim Ueq,
Uanis(C145) \\sim Ueq, Uanis(C150) \\sim Ueq, Uanis(C151) \\sim Ueq,
Uanis(C153) \\sim Ueq, Uanis(F31) \\sim Ueq, Uanis(F32) \\sim Ueq, Uanis(F33)
\\sim Ueq, Uanis(F33A) \\sim Ueq, Uanis(F32A) \\sim Ueq, Uanis(F31A) \\sim Ueq,
Uanis(F34) \\sim Ueq, Uanis(F36) \\sim Ueq, Uanis(F35A) \\sim Ueq, Uanis(F36A)
\\sim Ueq, Uanis(F34A) \\sim Ueq, Uanis(F37) \\sim Ueq, Uanis(F38) \\sim Ueq,
Uanis(F39) \\sim Ueq, Uanis(F40) \\sim Ueq, Uanis(F41) \\sim Ueq, Uanis(F42)
\\sim Ueq, Uanis(F43) \\sim Ueq, Uanis(F44) \\sim Ueq, Uanis(F45) \\sim Ueq,
Uanis(F46) \\sim Ueq, Uanis(F47) \\sim Ueq, Uanis(F48) \\sim Ueq, Uanis(C102)
\\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(F2) \\sim Ueq,
Uanis(F3) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C95)
\\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C98) \\sim Ueq,
Uanis(B1) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C107)
\\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq,
Uanis(F6) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C108)
\\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C122) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C109) \\sim Ueq,
Uanis(C112) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C120) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C110) \\sim Ueq,
Uanis(C111) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C118) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F8)
\\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq,
Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15)
\\sim Ueq, Uanis(F16) \\sim Ueq, Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq,
Uanis(F19) \\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F21) \\sim Ueq, Uanis(F22)
\\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F24) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C89A) = Uanis(C90) = Uanis(C84A) = Uanis(C88) = Uanis(C85A) = Uanis(C159)
= Uanis(C86) = Uanis(C155) = Uanis(C85) = Uanis(C84) = Uanis(C89) = Uanis(C88A)
= Uanis(C87) = Uanis(C86A) = Uanis(C31) = Uanis(C30)
Uanis(F34A) = Uanis(F34) = Uanis(F35A) = Uanis(F35) = Uanis(F36A) = Uanis(F36)
= Uanis(F32A) = Uanis(F32) = Uanis(F33A) = Uanis(F33) = Uanis(F31) =
Uanis(F31A) = Uanis(F43) = Uanis(F44) = Uanis(F45) = Uanis(F10) = Uanis(F12) =
Uanis(F11) = Uanis(F3) = Uanis(F2) = Uanis(F1) = Uanis(F28) = Uanis(F29) =
Uanis(F30) = Uanis(F26) = Uanis(F25) = Uanis(F27) = Uanis(F38) = Uanis(F14) =
Uanis(F13)
4. Others
 Fixed Sof: C89(0.75) C88(0.75) H88(0.75) C159(0.75) H159(0.75) C86(0.75)
 H86(0.75) C85(0.75) H85(0.75) C84(0.75) C90(0.75) F31(0.5) F32(0.5) F33(0.5)
 F34(0.5) F35(0.5) F36(0.5) C84A(0.25) C85A(0.25) C86A(0.25) H86A(0.25)
 C87(0.25) H87(0.25) C88A(0.25) H88A(0.25) C89A(0.25) H89A(0.25) C155(0.25)
 F35A(0.5) F36A(0.5) F34A(0.5) F33A(0.5) F32A(0.5) F31A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C15(H15), C16(H16), C17(H17), C18(H18),
 C22(H22), C23(H23), C24(H24), C25(H25), C29(H29), C30(H30), C31(H31), C32(H32),
  C36(H36), C37(H37), C38(H38), C39(H39), C43(H43), C44(H44), C45(H45),
 C46(H46), C50(H50), C51(H51), C52(H52), C53(H53), C57(H57), C58(H58), C59(H59),
  C60(H60), C64(H64), C65(H65), C66(H66), C67(H67), C71(H71), C72(H72),
 C73(H73), C74(H74), C78(H78), C79(H79), C80(H80), C81(H81), C88(H88),
 C159(H159), C86(H86), C85(H85), C124(H124), C127(H127), C130(H130), C132(H132),
  C135(H135), C138(H138), C140(H140), C143(H143), C146(H146), C148(H148),
 C151(H151), C154(H154), C92(H92), C95(H95), C98(H98), C100(H100), C103(H103),
 C106(H106), C108(H108), C111(H111), C114(H114), C116(H116), C119(H119),
 C122(H122), C86A(H86A), C87(H87), C88A(H88A), C89A(H89A)
5.b Fitted hexagon refined as free rotating group:
 C84A(C85A,C86A,C87,C88A,C89A)
5.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C27(H27A,H27B,H27C), C34(H34A,H34B,
 H34C), C41(H41A,H41B,H41C), C48(H48A,H48B,H48C), C55(H55A,H55B,H55C), C62(H62A,
 H62B,H62C), C69(H69A,H69B,H69C), C76(H76A,H76B,H76C), C83(H83A,H83B,H83C),
 C90(H90A,H90B,H90C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              36864
_shelx_fab_checksum              1357
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'