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_1576873
_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         'C98 H108 F4 N8 O4 S4, C H Cl3'
_chemical_formula_sum            'C99 H109 Cl3 F4 N8 O4 S4'
_chemical_formula_weight         1785.53
_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                68.881(4)
_cell_angle_beta                 81.564(3)
_cell_angle_gamma                71.711(4)
_cell_formula_units_Z            2
_cell_length_a                   12.9602(6)
_cell_length_b                   17.7674(12)
_cell_length_c                   23.0842(11)
_cell_measurement_reflns_used    3528
_cell_measurement_temperature    180.00
_cell_measurement_theta_max      64.89
_cell_measurement_theta_min      2.78
_cell_volume                     4704.7(5)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'Bruker Apex3'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      180.00
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.1204
_diffrn_reflns_av_unetI/netI     0.1675
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            28058
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        44.492
_diffrn_reflns_theta_max         44.492
_diffrn_reflns_theta_min         2.053
_diffrn_source_current           1.01
_diffrn_source_power             0.0505
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.218
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.5031
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1303 before and 0.0788 after correction.
The Ratio of minimum to maximum transmission is 0.6683.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_description       block
_exptl_crystal_F_000             1884
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.087
_refine_diff_density_min         -1.097
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.107
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1077
_refine_ls_number_reflns         7394
_refine_ls_number_restraints     2361
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.2659
_refine_ls_R_factor_gt           0.2114
_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^)+(0.0900P)^2^+110.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4676
_refine_ls_wR_factor_ref         0.5053
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4364
_reflns_number_total             7394
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ee07321a2.cif
_cod_data_source_block           che-me
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               1576873
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.777
_shelx_estimated_absorpt_t_min   0.718
_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
 C79-C80
 1.5 with sigma of 0.02
 C57-C58 = C57-C56
 1.5 with sigma of 0.02
 C96-C95 = C97-C96
 1.5 with sigma of 0.02
 C64-C63 = C63-C62 = C61-C62 = C61-C60 = C59-C60 = C59-C54
 1.5 with sigma of 0.01
 O4-C33
 1.28 with sigma of 0.02
 C91-C92
 1.5 with sigma of 0.02
 C93-C94
 1.5 with sigma of 0.02
 C74-C75
 1.5 with sigma of 0.02
 C32-C28
 1.5 with sigma of 0.02
 N6-C52
 1.25 with sigma of 0.02
 C32-O4
 1.28 with sigma of 0.02
 O3-C32
 1.28 with sigma of 0.02
 C94-C97
 2.8 with sigma of 0.04
 H40-H87B
 2.2 with sigma of 0.04
 C56-C55 \\sim C55-C54 \\sim C57-C56 \\sim C58-C57
 with sigma of 0.02
 C97-C96 \\sim C96-C95 \\sim C95-C94 \\sim C93-C94 \\sim C92-C93 \\sim C92-C91
\\sim C91-C90 \\sim C90-C89
 \\sim C88-C89 \\sim C88-C87
 with sigma of 0.02
 C64-C63 \\sim C63-C62 \\sim C61-C62 \\sim C61-C60 \\sim C59-C60 \\sim C59-C54
 with sigma of 0.02
 C69-C68 \\sim C70-C69 \\sim C68-C67 \\sim C67-C66
 with sigma of 0.02
 C86-C85 \\sim C84-C85 \\sim C83-C84 \\sim C83-C82 \\sim C82-C81 \\sim C81-C80
\\sim C80-C79 \\sim C77-C78
 \\sim C79-C78 \\sim C77-C76 \\sim C76-C15
 with sigma of 0.02
 C41-C42 \\sim C49-C41
 with sigma of 0.02
 C51-C50 \\sim C52-C50
 with sigma of 0.02
 C20-C25 \\sim C25-C24 \\sim C23-C24 \\sim C22-C23 \\sim C22-C21 \\sim C21-C20
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N3 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim
C95 \\sim C96 \\sim C97: within 3A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 3A
N4 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C98: within 3A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3A
S1 \\sim S2 \\sim S3 \\sim S4 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim O1
\\sim O2 \\sim O3 \\sim O4 \\sim N1 \\sim N2 \\sim N3 \\sim N3 \\sim N4 \\sim
N5 \\sim N6 \\sim N7 \\sim N8 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5
\\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13
\\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21
\\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C31 \\sim C30 \\sim C29
\\sim C28 \\sim C27 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37
\\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C45 \\sim C46 \\sim C47 \\sim C48
\\sim C43 \\sim C44 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53: within
3.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.5A
C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim
C84 \\sim C85 \\sim C86: within 3A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 3A
4.a Riding coordinates:
 C33(H33A,H33B,H33C), C58(H58A,H58B,H58C), C64(H64A,H64B,H64C), C70(H70A,H70B,
 H70C), C87(H87A,H87B), C88(H88A,H88B), C97(H97A,H97B,H97C)
4.b Ternary CH refined with riding coordinates:
 C54(H54), C66(H66), C99(H99)
4.c Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C59(H59A,
 H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B),
 C65(H65A,H65B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B), C71(H71A,H71B),
  C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C76(H76A,H76B), C77(H77A,
 H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B),
 C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C89(H89A,H89B),
  C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,
 H94B), C95(H95A,H95B), C96(H96A,H96B), C98(H98A,H98B)
4.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C13(H13), C30(H30), C29(H29), C27(H27), C40(H40), C47(H47),
 C44(H44)
4.e Fitted hexagon refined as free rotating group:
 C26(C31,C30,C29,C28,C27), C45(C46,C47,C48,C43,C44)
4.f Idealised Me refined as rotating group:
 C75(H75A,H75B,H75C), C86(H86A,H86B,H86C)
;
_shelx_res_checksum              60409
_olex2_submission_special_instructions 'No special instructions were received'