Synergistic Steric-Dipole Modulation via Stepwise Trifluoromethyl Substitution Enables Active-Layer Hierarchical Assembly and >20% Power Conversion Efficiency in Organic Photovoltaic Devices
Wang, Jie; Chen, Xin; Huo, Jingyi; Yang, Jiong; Li, Longyu; Shi, Wendi; Bian, Ruibin; Zhao, Wenkai; Long, Guankui; Yao, Zhaoyang; Li, Chenxi; Wan, Xiangjian; Chen, Yongsheng; Energy & Environmental Science  (2026) –; doi:10.1039/D5EE07321A

data_1576875
_publ_section_title
;
 Synergistic Steric-Dipole Modulation via Stepwise Trifluoromethyl
 Substitution Enables Active-Layer Hierarchical Assembly and &gt;20% Power
 Conversion Efficiency in Organic Photovoltaic Devices
;
_journal_name_full               'Energy &amp; Environmental Science'
_journal_paper_doi               10.1039/D5EE07321A
_journal_year                    2026
_chemical_formula_moiety         'C100 H106 F10 N8 O4 S4, 1[CHCl3]'
_chemical_formula_sum            'C101 H107 Cl3 F10 N8 O4 S4'
_chemical_formula_weight         1921.53
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2026-01-23
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-02-05 deposited with the CCDC.	2026-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                99.692(4)
_cell_angle_beta                 98.243(3)
_cell_angle_gamma                94.310(4)
_cell_formula_units_Z            2
_cell_length_a                   12.8673(9)
_cell_length_b                   16.3829(12)
_cell_length_c                   23.2488(16)
_cell_measurement_reflns_used    7730
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      47.16
_cell_measurement_theta_min      2.75
_cell_volume                     4756.2(6)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'Bruker Apex3'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0624
_diffrn_reflns_av_unetI/netI     0.0765
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            23262
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        44.490
_diffrn_reflns_theta_max         44.490
_diffrn_reflns_theta_min         1.952
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.327
_exptl_absorpt_correction_T_max  0.2910
_exptl_absorpt_correction_T_min  0.1461
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1314 before and 0.0794 after correction.
The Ratio of minimum to maximum transmission is 0.5021.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       needle
_exptl_crystal_F_000             2012
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.057
_refine_diff_density_min         -0.897
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.199
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1102
_refine_ls_number_reflns         7487
_refine_ls_number_restraints     1297
_refine_ls_restrained_S_all      1.225
_refine_ls_R_factor_all          0.2113
_refine_ls_R_factor_gt           0.1742
_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^)+(0.1000P)^2^+50.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3995
_refine_ls_wR_factor_ref         0.4216
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4964
_reflns_number_total             7487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ee07321a2.cif
_cod_data_source_block           che-6f
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               1576875
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.693
_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
 C55-C15 = C56-C55 = C57-C56 = C58-C57 = C59-C58 = C59-C60 = C61-C60 = C61-C62
 = C63-C62 = C63-C64 = C65-C64
 1.5 with sigma of 0.01
 C68-C67 = C69-C68 = C70-C69 = C71-C70 = C72-C67 = C73-C72 = C74-C73 = C74-C75
 = C76-C75 = C77-C76 = C80-C79 = C81-C80 = C82-C81 = C82-C83 = C79-C84 = C85-
 C84 = C86-C85 = C87-C86 = C88-C87 = C89-C88
 1.5 with sigma of 0.01
 C100-C99 = C98-C99 = C97-C98 = C97-C96 = C96-C95 = C95-C94 = C93-C94 = C93-
 C92 = C92-C91 = C91-C90
 1.5 with sigma of 0.01
 C75-C76
 1.5 with sigma of 0.01
 C54-C52
 1.5 with sigma of 0.01
 O4-C52 = O4-C51
 1.3 with sigma of 0.01
 O3-C51
 1.25 with sigma of 0.01
 C54-C52 = C52-C53
 1.5 with sigma of 0.01
 F10-C54
 1.35 with sigma of 0.02
 F9-C54 = F8-C54
 1.35 with sigma of 0.02
 F6-C53 = F5-C53 = F7-C53
 1.35 with sigma of 0.02
 F8-F10
 2.3 with sigma of 0.02
 F9-F10
 2.3 with sigma of 0.02
 F9-F8
 2.3 with sigma of 0.02
 N4-C43 = N4-C45 = N5-C46 = N5-C44
 1.35 with sigma of 0.02
 C8-C12
 1.5 with sigma of 0.01
 C77-C75
 2.4 with sigma of 0.04
 C100-C98
 2.5 with sigma of 0.04
 C99-C97
 2.5 with sigma of 0.04
 C98-C96
 2.5 with sigma of 0.04
 C89-C87
 2.4 with sigma of 0.04
 C77-C76 \\sim C76-C75 \\sim C75-C74
 with sigma of 0.02
 C58-C57 \\sim C59-C58 \\sim C57-C56
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C69 \\sim C72 \\sim C73 \\sim C70 \\sim C74 \\sim C71 \\sim C75 \\sim C76 \\sim
C77: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C77 \\sim C76 \\sim C75 \\sim C74 \\sim C73 \\sim C72 \\sim C67 \\sim C66 \\sim
C68 \\sim C69 \\sim C70 \\sim C71: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C94 \\sim C96 \\sim C100 \\sim C98 \\sim C97 \\sim C95 \\sim C99: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C7 \\sim C6 \\sim C5 \\sim C4 \\sim C3 \\sim C2 \\sim C1 \\sim C12 \\sim C8
\\sim C9 \\sim F2 \\sim C10: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
C85 \\sim C80 \\sim C86 \\sim C87 \\sim C81 \\sim C83 \\sim C82 \\sim C88 \\sim
C89: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C56 \\sim C57 \\sim C60 \\sim C62 \\sim C61 \\sim C58 \\sim C64 \\sim C59 \\sim
C63 \\sim C65: within 3A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 3A
C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim O4 \\sim O3 \\sim
C51 \\sim F10 \\sim F7 \\sim F6 \\sim F9 \\sim F5 \\sim F8 \\sim C52 \\sim C54
\\sim C53: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 3A
C37 \\sim C38 \\sim C33 \\sim C34 \\sim C35 \\sim C36: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
N4 \\sim N5 \\sim C46 \\sim C45 \\sim C50 \\sim C49 \\sim C48 \\sim C47 \\sim
C51 \\sim O3 \\sim O4 \\sim F5 \\sim C52 \\sim F7 \\sim F6 \\sim C53 \\sim F10
\\sim F9 \\sim F8 \\sim C54 \\sim C43 \\sim C20 \\sim C44 \\sim C23 \\sim C22
\\sim C21 \\sim C19 \\sim C18 \\sim N3 \\sim C17 \\sim C16 \\sim S2 \\sim C15
\\sim C14 \\sim S1 \\sim C24 \\sim C25 \\sim N6 \\sim C26 \\sim C27 \\sim S3
\\sim C28 \\sim C29 \\sim S4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97 \\sim C98 \\sim C99 \\sim
C100 \\sim C91 \\sim C90: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(N4) \\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C91) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C93) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4.a Riding coordinates:
 C66(H66A,H66B), C94(H94A,H94B), C83(H83A,H83B,H83C), C100(H10A,H10B,H10C),
 C98(H98A,H98B), C77(H77A,H77B,H77C)
4.b Ternary CH refined with riding coordinates:
 C79(H79), C67(H67), C52(H52)
4.c Secondary CH2 refined with riding coordinates:
 C90(H90A,H90B), C78(H78A,H78B), C55(H55A,H55B), C84(H84A,H84B), C68(H68A,
 H68B), C85(H85A,H85B), C69(H69A,H69B), C72(H72A,H72B), C56(H56A,H56B),
 C91(H91A,H91B), C80(H80A,H80B), C57(H57A,H57B), C92(H92A,H92B), C73(H73A,H73B),
  C86(H86A,H86B), C70(H70A,H70B), C60(H60A,H60B), C87(H87A,H87B), C62(H62A,
 H62B), C61(H61A,H61B), C81(H81A,H81B), C58(H58A,H58B), C64(H64A,H64B),
 C59(H59A,H59B), C63(H63A,H63B), C93(H93A,H93B), C74(H74A,H74B), C82(H82A,H82B),
  C96(H96A,H96B), C97(H97A,H97B), C95(H95A,H95B), C99(H99A,H99B), C88(H88A,
 H88B), C75(H75A,H75B), C76(H76A,H76B)
4.d Aromatic/amide H refined with riding coordinates:
 C50(H50), C48(H48), C47(H47), C30(H30), C37(H37), C34(H34), C13(H13), C3(H3),
 C6(H6)
4.e Fitted hexagon refined as free rotating group:
 C46(C45,C50,C49,C48,C47), C37(C36,C35,C34,C33,C38), C2(C3,C4,C5,C6,C7)
4.f Idealised Me refined as rotating group:
 C71(H71A,H71B,H71C), C65(H65A,H65B,H65C), C89(H89A,H89B,H89C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 109 electrons were 
found in a volume of 431\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[CHCl3] per Asymmetric Unit 
which account for 36 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46004
_shelx_fab_checksum              60579
_olex2_submission_special_instructions 'No special instructions were received'