Non-fullerene acceptors with direct and indirect hexa-fluorination afford >17% efficiency in polymer solar cells
Li, Guoping; Feng, Liang-Wen; Mukherjee, Subhrangsu; Jones, Leighton O.; Jacobberger, Robert M.; Huang, Wei; Young, Ryan M.; Pankow, Robert M.; Zhu, Weigang; Lu, Norman; Kohlstedt, Kevin L.; Sangwan, Vinod K.; Wasielewski, Michael R.; Hersam, Mark C.; Schatz, George C.; DeLongchamp, Dean M.; Facchetti, Antonio; Marks, Tobin J.; Energy & Environmental Science 15 (2022) 645–659; doi:10.1039/D1EE03225A

data_1565982
_publ_section_title
;
 Non-fullerene acceptors with direct and indirect hexa-fluorination afford
 &gt;17% efficiency in polymer solar cells
;
_journal_issue                   2
_journal_name_full               'Energy &amp; Environmental Science'
_journal_page_first              645
_journal_page_last               659
_journal_paper_doi               10.1039/D1EE03225A
_journal_volume                  15
_journal_year                    2022
_chemical_formula_moiety         'C98 H102 F6 N8 O2 S5'
_chemical_formula_sum            'C98 H102 F6 N8 O2 S5'
_chemical_formula_weight         1698.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-09-13 deposited with the CCDC.	2021-12-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.2500(10)
_cell_angle_gamma                90
_cell_formula_units_Z            10
_cell_length_a                   24.0563(4)
_cell_length_b                   25.5964(4)
_cell_length_c                   43.2943(7)
_cell_measurement_reflns_used    32365
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      50.2930
_cell_measurement_theta_min      2.5270
_cell_volume                     26615.8(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.75a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.75a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.75a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -13.00  13.00   0.50   20.00    --   -0.08  17.00-172.00   52
  2  \w     45.00  71.00   0.50   20.00    --   -0.08  17.00-172.00   52
  3  \w     -1.00  27.00   0.50   50.00    --   55.50 -17.00  17.00   56
  4  \w     42.00 129.00   0.50   50.00    --   55.50  17.00-172.00  174
  5  \w   -120.00 -64.00   0.50   50.00    --  -55.65 -17.00  17.00  112
  6  \w    -23.00   2.00   0.50   50.00    --  -55.65  17.00-172.00   50
  7  \w    -35.00 -10.00   0.50   20.00    --   -0.08 -17.00  17.00   50
  8  \w      7.00  33.00   0.50   20.00    --   -0.08 -99.00-120.00   52
  9  \w     19.00  45.00   0.50   50.00    --   55.50-125.00 -90.00   52
 10  \w     -1.00  43.00   0.50   50.00    --   55.50 -37.00 -30.00   88
 11  \w     34.00  91.00   0.50   50.00    --   55.50-125.00   0.00  114
 12  \w     34.00 102.00   0.50   50.00    --   55.50-125.00  30.00  136
 13  \w      6.00  68.00   0.50   50.00    --   55.50 -57.00   0.00  124
 14  \w    -19.00  19.00   0.50   50.00    --   55.50 -19.00-120.00   76
 15  \w    -16.00  61.00   0.50   50.00    --   55.50 -57.00 -90.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0054097000
_diffrn_orient_matrix_UB_12      -0.0027840000
_diffrn_orient_matrix_UB_13      0.0355991000
_diffrn_orient_matrix_UB_21      -0.0623820000
_diffrn_orient_matrix_UB_22      0.0128211000
_diffrn_orient_matrix_UB_23      0.0013655000
_diffrn_orient_matrix_UB_31      -0.0137990000
_diffrn_orient_matrix_UB_32      -0.0587365000
_diffrn_orient_matrix_UB_33      -0.0014287000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0298
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            107376
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        51.863
_diffrn_reflns_theta_max         51.863
_diffrn_reflns_theta_min         2.523
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.454
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27578
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.75a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.059
_exptl_crystal_description       block
_exptl_crystal_F_000             8960
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.163
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.773
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.783
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2700
_refine_ls_number_reflns         29121
_refine_ls_number_restraints     4611
_refine_ls_restrained_S_all      1.750
_refine_ls_R_factor_all          0.2087
_refine_ls_R_factor_gt           0.1694
_refine_ls_shift/su_max          0.000
_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          0.4542
_refine_ls_wR_factor_ref         0.4809
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15632
_reflns_number_total             29121
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ee03225a2.cif
_cod_data_source_block           cx1994
_cod_depositor_comments
'Adding full bibliography for 1565981--1565982.cif.'
_cod_database_code               1565982
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C98H104F6N8O2S5
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.797
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     50.38
_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
 C53-C10 = C54-C53 = C55-C54 = C56-C55 = C57-C56 = C58-C57 = C59-C58 = C60-C59
 = C61-C60 = C62-C61 = C63-C62 = C65-C64 = C72-C65 = C73-C72 = C74-C73 = C75-
 C74 = C66-C65 = C67-C66 = C68-C67 = C69-C68 = C70-C69 = C71-C70 = C77-C76 =
 C84-C77 = C78-C77 = C79-C78 = C80-C79 = C81-C80 = C82-C81 = C83-C82 = C85-C84 =
  C86-C85 = C87-C86 = C88-C1 = C89-C88 = C90-C89 = C91-C90 = C92-C91 = C93-C92 =
  C94-C93 = C95-C94 = C96-C95 = C97-C96 = C98-C97
 1.54 with sigma of 0.02
 C96-C98 = C95-C97 = C92-C94 = C93-C91 = C90-C88 = C89-C1 = C87-C85 = C86-C84 =
  C83-C81 = C82-C80 = C79-C77 = C76-C78 = C75-C73 = C74-C72 = C71-C69 = C70-C68
 = C67-C65 = C66-C64 = C61-C63 = C62-C60 = C59-C57 = C58-C56 = C55-C53 = C54-C10
 2.4 with sigma of 0.02
 C53A-C10A = C54A-C53A = C55A-C54A = C56A-C55A = C57A-C56A = C58A-C57A = C59A-
 C58A = C60A-C59A = C61A-C60A = C62A-C61A = C63A-C62A = C71A-C70A = C70A-C69A =
 C69A-C68A = C68A-C67A = C67A-C66A = C66A-C65A = C72A-C65A = C73A-C72A = C74A-
 C73A = C75A-C74A = C65A-C64A = C77A-C76A = C78A-C77A = C79A-C78A = C80A-C79A =
 C81A-C80A = C83A-C82A = C82A-C81A = C84A-C77A = C85A-C84A = C86A-C85A = C87A-
 C86A = C88A-C1A = C89A-C88A = C90A-C89A = C91A-C90A = C92A-C91A = C93A-C92A =
 C94A-C93A = C95A-C94A = C96A-C95A = C97A-C96A = C98A-C97A
 1.54 with sigma of 0.02
 C63A-C61A = C62A-C60A = C59A-C57A = C58A-C56A = C55A-C53A = C10A-C54A = C73A-
 C75A = C74A-C72A = C64A-C66A = C65A-C67A = C68A-C70A = C71A-C69A = C87A-C85A =
 C86A-C84A = C83A-C81A = C82A-C80A = C79A-C77A = C78A-C76A = C98A-C96A = C97A-
 C95A = C94A-C92A = C93A-C91A = C90A-C88A = C89A-C1A
 2.4 with sigma of 0.02
 C39B-C38B = C40B-C39B = C41B-C40B = C42B-C41B = C43B-C42B = C44B-C43B = C45B-
 C44B = C46B-C39B = C47B-C46B = C48B-C47B = C49B-C48B = C5B-C27B = C28B-C27B =
 C29B-C28B = C30B-C29B = C31B-C30B = C32B-C31B = C33B-C32B = C34B-C33B = C35B-
 C34B = C36B-C35B = C37B-C36B
 1.54 with sigma of 0.02
 C49B-C47B = C48B-C46B = C45B-C43B = C44B-C42B = C41B-C39B = C40B-C38B = C37B-
 C35B = C36B-C34B = C33B-C31B = C32B-C30B = C29B-C27B = C28B-C5B
 2.4 with sigma of 0.02
 C80-C78
 2.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(F3E)=1-FVAR(1)
 Sof(F3A)=FVAR(1)
 Sof(F1B)=1-FVAR(2)
 Sof(F05C)=FVAR(2)
 Sof(F3D)=1-FVAR(3)
 Sof(F3)=FVAR(3)
 Sof(F4)=1-FVAR(4)
 Sof(F4D)=FVAR(4)
 Sof(F4A)=1-FVAR(5)
 Sof(F4E)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C65(H65), C77(H77), C65A(H65A), C77A(H77A), C39B(H39B)
6.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,
 H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B),
 C62(H62A,H62B), C64(H64A,H64B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B),
  C69(H69A,H69B), C70(H70A,H70B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,
 H74B), C76(H76A,H76B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B),
 C81(H81A,H81B), C82(H82A,H82B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B),
  C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,
 H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B),
 C97(H97A,H97B), C53A(H53C,H53D), C54A(H54C,H54D), C55A(H55C,H55D), C56A(H56C,
 H56D), C57A(H57C,H57D), C58A(H58C,H58D), C59A(H59C,H59D), C60A(H60C,H60D),
 C61A(H61C,H61D), C62A(H62C,H62D), C64A(H64C,H64D), C66A(H66C,H66D), C67A(H67C,
 H67D), C68A(H68C,H68D), C69A(H69C,H69D), C70A(H70C,H70D), C72A(H72C,H72D),
 C73A(H73C,H73D), C74A(H74C,H74D), C76A(H76C,H76D), C78A(H78C,H78D), C79A(H79C,
 H79D), C80A(H80C,H80D), C81A(H81C,H81D), C82A(H82C,H82D), C84A(H84C,H84D),
 C85A(H85C,H85D), C86A(H86C,H86D), C88A(H88C,H88D), C89A(H89C,H89D), C90A(H90C,
 H90D), C91A(H91C,H91D), C92A(H92C,H92D), C93A(H93C,H93D), C94A(H94C,H94D),
 C95A(H95C,H95D), C96A(H96C,H96D), C97A(H97C,H97D), C27B(H27A,H27B), C28B(H28A,
 H28B), C29B(H29A,H29B), C30B(H30B,H30C), C31B(H31A,H31B), C32B(H32A,H32B),
 C33B(H33A,H33B), C34B(H34A,H34B), C35B(H35A,H35B), C36B(H36B,H36C), C38B(H38A,
 H38B), C40B(H40B,H40C), C41B(H41A,H41B), C42B(H42A,H42B), C43B(H43A,H43B),
 C44B(H44A,H44B), C46B(H46A,H46B), C47B(H47B,H47C), C48B(H48A,H48B)
6.c Me refined with riding coordinates:
 C63(H63A,H63B,H63C), C71(H71A,H71B,H71C), C75(H75A,H75B,H75C), C83(H83A,H83B,
 H83C), C87(H87A,H87B,H87C), C98(H98A,H98B,H98C), C63A(H63D,H63E,H63F),
 C71A(H71D,H71E,H71F), C75A(H75D,H75E,H75F), C83A(H83D,H83E,H83F), C87A(H87D,
 H87E,H87F), C98A(H98D,H98E,H98F), C37B(H37A,H37B,H37C), C45B(H45A,H45B,H45C),
 C49B(H49A,H49B,H49C)
6.d Aromatic/amide H refined with riding coordinates:
 C19(H19), C23(H23), C30(H30), C36(H36), C40(H40), C47(H47), C19A(H19A),
 C23A(H23A), C30A(H30A), C36A(H36A), C40A(H40A), C47A(H47A), C10B(H10B),
 C14B(H14B), C21B(H21B)
6.e Fitted hexagon refined as free rotating group:
 C46(C41,C42,C43,C44,C45), C24A(C25A,C26A,C27A,C28A,C29A)
;
_shelx_res_checksum              46807
_shelx_fab_checksum              53459
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a   with Paratone oil'
_olex2_submission_original_sample_id cx1994
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.111
_oxdiff_exptl_absorpt_empirical_full_min 0.596