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_1576874
_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         '2(C99 H107 F7 N8 O4 S4), C H Cl3'
_chemical_formula_sum            'C199 H215 Cl3 F14 N16 O8 S8'
_chemical_formula_weight         3587.69
_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                68.582(4)
_cell_angle_beta                 81.345(3)
_cell_angle_gamma                71.646(3)
_cell_formula_units_Z            1
_cell_length_a                   12.9860(6)
_cell_length_b                   17.7668(11)
_cell_length_c                   23.1063(12)
_cell_measurement_reflns_used    3700
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      52.45
_cell_measurement_theta_min      2.79
_cell_volume                     4706.6(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  'XL  (Sheldrick, 2008)'
_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 0.998
_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  0.1067
_diffrn_reflns_av_unetI/netI     0.1039
_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       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            33755
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        42.092
_diffrn_reflns_theta_max         42.092
_diffrn_reflns_theta_min         2.055
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.884
_exptl_absorpt_correction_T_max  0.7507
_exptl_absorpt_correction_T_min  0.5271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1332 before and 0.0748 after correction.
The Ratio of minimum to maximum transmission is 0.7021.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       plate
_exptl_crystal_F_000             1890
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.916
_refine_diff_density_min         -0.820
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1088
_refine_ls_number_reflns         6478
_refine_ls_number_restraints     1773
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.2580
_refine_ls_R_factor_gt           0.2031
_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^+130.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4447
_refine_ls_wR_factor_ref         0.4794
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3893
_reflns_number_total             6478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ee07321a2.cif
_cod_data_source_block           che-3f
_cod_original_cell_volume        4706.7(5)
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               1576874
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.753
_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
 C87-C88 = C87-C86 = C86-C85 = C85-C84 = C84-C83 = C78-C83 = C79-C78 = C80-C79
 = C81-C80 = C82-C81
 1.52 with sigma of 0.01
 C55-C54 = C55-C56 = C57-C56 = C57-C58 = C59-C58 = C59-C60 = C60-C61 = C62-C61
 = C62-C63 = C64-C63
 1.52 with sigma of 0.01
 C37-C36
 1.52 with sigma of 0.01
 C90-C89 = C91-C90 = C91-C92 = C92-C93 = C94-C93 = C94-C95 = C96-C95 = C96-C97
 = C97-C98
 1.52 with sigma of 0.01
 C63-C64 = C63-C62
 1.52 with sigma of 0.01
 O4-C36 = O4-C35 = O3-C35
 1.25 with sigma of 0.02
 C98-C99
 1.52 with sigma of 0.01
 C73-C66 = C74-C73 = C75-C74 = C76-C75 = C67-C66 = C68-C67 = C69-C68 = C69-C70
 = C71-C70 = C72-C71
 1.52 with sigma of 0.01
 C48-C8 = C48-C49 = C48-C50
 1.52 with sigma of 0.01
 O3-C35
 1.3 with sigma of 0.02
 O4-C35
 1.35 with sigma of 0.02
 F5-C37 = F6-C37 = F7-C37
 1.4 with sigma of 0.02
 C35-C32
 1.48 with sigma of 0.02
 C40-C39
 1.52 with sigma of 0.01
 C53-C51 = C52-C51
 1.5 with sigma of 0.01
 N7-C53 = N8-C52
 1.1 with sigma of 0.01
 H38-H89A
 2.2 with sigma of 0.04
 H88B-H72B_$1
 2.2 with sigma of 0.04
 F6-F5
 2.2 with sigma of 0.04
 F6-F7
 2.2 with sigma of 0.04
 F7-F5
 2.2 with sigma of 0.04
 O4-C36 \\sim O4-C35
 with sigma of 0.02
 F5-C37 \\sim F6-C37 \\sim F7-C37
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim
C97 \\sim C98 \\sim C99: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C29 \\sim C35 \\sim O3 \\sim
O4 \\sim C36 \\sim C37 \\sim F5 \\sim F6 \\sim F7 \\sim N6 \\sim N5 \\sim C21
\\sim C22 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C23 \\sim C24 \\sim N4
\\sim S3 \\sim C26 \\sim C27 \\sim C28 \\sim S4 \\sim C25 \\sim C38 \\sim C39
\\sim C47 \\sim O2 \\sim C46 \\sim C45 \\sim C44 \\sim C43 \\sim C42 \\sim C41
\\sim F4 \\sim F3 \\sim C40 \\sim C51 \\sim C53 \\sim N7 \\sim C52 \\sim N8
\\sim N3 \\sim C15 \\sim C16 \\sim S2 \\sim C13 \\sim C14 \\sim S1 \\sim C11
\\sim C12 \\sim C10 \\sim C9 \\sim C8 \\sim C48 \\sim C50 \\sim N2 \\sim C49
\\sim N1 \\sim C7 \\sim C6 \\sim C5 \\sim C4 \\sim C3 \\sim C2 \\sim C1 \\sim
O1 \\sim F2 \\sim F1: within 2.5A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2.5A
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
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim
C73 \\sim C74 \\sim C75 \\sim C76: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
F5 \\sim F6 \\sim F7 \\sim O3 \\sim O4 \\sim C35 \\sim C36 \\sim C37: within 3A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim
C85 \\sim C86 \\sim C87 \\sim C88: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
F3 \\sim F4 \\sim C41 \\sim C46 \\sim C45 \\sim C44 \\sim C43 \\sim C42: within
3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
Cl1 \\sim C100 \\sim Cl3 \\sim Cl2: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C53) \\sim Ueq, Uanis(N7) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(N8)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C51) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C43) \\sim Ueq,
Uanis(C42) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C47) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C28)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: Cl1(0.5) Cl2(0.5) Cl3(0.5) C100(0.5) H100(0.5)
5.a Riding coordinates:
 C36(H36A,H36B), C54(H54A,H54B), C61(H61A,H61B), C62(H62A,H62B), C64(H64A,H64B,
 H64C), C65(H65A,H65B), C76(H76A,H76B,H76C), C82(H82A,H82B,H82C), C88(H88A,H88B,
 H88C), C89(H89A,H89B), C90(H90A,H90B), C93(H93A,H93B), C99(H99A,H99B,H99C)
5.b Ternary CH refined with riding coordinates:
 C66(H66), C78(H78), C100(H100)
5.c Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,
 H59B), C60(H60A,H60B), C63(H63A,H63B), C67(H67A,H67B), C68(H68A,H68B),
 C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B), C73(H73A,H73B), C74(H74A,H74B),
  C75(H75A,H75B), C77(H77A,H77B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,
 H81B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B),
 C87(H87A,H87B), C91(H91A,H91B), C92(H92A,H92B), C94(H94A,H94B), C95(H95A,H95B),
  C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B)
5.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C3(H3), C10(H10), C31(H31), C34(H34), C33(H33), C38(H38), C45(H45),
 C42(H42)
5.e Fitted hexagon refined as free rotating group:
 C7(C6,C5,C4,C3,C2), C22(C17,C18,C19,C20,C21), C32(C31,C30,C29,C34,C33),
 C41(C46,C45,C44,C43,C42)
5.f Idealised Me refined as rotating group:
 C72(H72A,H72B,H72C)
;
_shelx_res_checksum              93164
_olex2_submission_special_instructions 'No special instructions were received'