Cyclopentadithiophene-Based Hole-Transporting Material for Highly Stable Perovskite Solar Cells with Stabilized Efficiencies Approaching 21%
Akin, Seckin; Bauer, Michael; Uchida, Ryusuke; Arora, Neha; Jacopin, Gwenole; Liu, Yuhang; Hertel, Dirk; Meerholz, Klaus; Mena-Osteritz, Elena; Bäuerle, Peter; Zakeeruddin, Shaik Mohammed; Dar, M. Ibrahim; Grätzel, Michael; ACS Applied Energy Materials  (2020) –; doi:10.1021/acsaem.0c00811

data_4517875
_publ_section_title
;
 Cyclopentadithiophene-Based Hole-Transporting Material for Highly Stable
 Perovskite Solar Cells with Stabilized Efficiencies Approaching 21%
;
_journal_name_full               'ACS Applied Energy Materials'
_journal_paper_doi               10.1021/acsaem.0c00811
_journal_year                    2020
_chemical_formula_moiety         'C H Cl3, C87 H78 N4 O10'
_chemical_formula_sum            'C88 H79 Cl3 N4 O10'
_chemical_formula_weight         1458.90
_chemical_name_systematic
4,4',4'',4'''-(5,5-dimethoxycyclopenta-1,3-diene-1,2,3,4-tetrayl)tetrakis(N,N-bis(4-methoxyphenyl)aniline)
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                107.709(3)
_cell_angle_beta                 95.3396(19)
_cell_angle_gamma                90.349(2)
_cell_formula_units_Z            2
_cell_length_a                   10.8185(2)
_cell_length_b                   16.2139(5)
_cell_length_c                   22.5926(6)
_cell_measurement_reflns_used    11357
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.9340
_cell_measurement_theta_min      2.8450
_cell_volume                     3756.32(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3385
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.964
_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   -106.00 -20.00   1.00    1.00    --  -42.93 -57.00-180.00   86
  2  \w   -122.00 -80.00   1.00    1.00    --  -42.93 -99.00 -60.00   42
  3  \w    -71.00  30.00   1.00    1.00    --  -42.93  57.00 -30.00  101
  4  \w   -124.00 -99.00   1.00    1.00    --  -42.93 -99.00   0.00   25
  5  \w   -124.00 -85.00   1.00    1.00    --  -42.93 -99.00-120.00   39
  6  \w     24.00  90.00   1.00    1.00    --   42.93-125.00 120.00   66
  7  \w     74.00  99.00   1.00    1.00    --   42.93-125.00 -30.00   25
  8  \w     84.00 177.00   1.00    3.16    --  107.13  45.00 150.00   93
  9  \w     48.00 135.00   1.00    3.16    --  107.13 -61.00 -60.00   87
 10  \w    107.00 169.00   1.00    3.16    --  107.13 125.00  90.00   62
 11  \w     57.00 102.00   1.00    3.16    --  107.13-125.00 -90.00   45
 12  \w     34.00 117.00   1.00    3.16    --  107.13 -30.00 120.00   83
 13  \w     66.00 117.00   1.00    3.16    --  107.13-125.00-180.00   51
 14  \w     37.00 117.00   1.00    3.16    --  107.13-125.00 -30.00   80
 15  \w     75.00 104.00   1.00    3.16    --  107.13-125.00  90.00   29
 16  \w    117.00 168.00   1.00    3.16    --  107.13 102.00  39.00   51
 17  \w     32.00 152.00   1.00    3.16    --  107.13 -15.00 -30.00  120
 18  \w     32.00 124.00   1.00    3.16    --  107.13 -77.00  90.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0593759000
_diffrn_orient_matrix_UB_12      0.0135139000
_diffrn_orient_matrix_UB_13      0.0670932000
_diffrn_orient_matrix_UB_21      0.0142477000
_diffrn_orient_matrix_UB_22      -0.0985091000
_diffrn_orient_matrix_UB_23      -0.0149663000
_diffrn_orient_matrix_UB_31      0.1294349000
_diffrn_orient_matrix_UB_32      0.0086468000
_diffrn_orient_matrix_UB_33      -0.0212052000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0500
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            27806
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.161
_diffrn_reflns_theta_min         2.863
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.619
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71400
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             1532
_exptl_crystal_preparation       'Solved in CHCl3'
_exptl_crystal_recrystallization_method
'Solution layered with n-hexane. Antisolvent vapor diffusion crystallization methos'
_exptl_crystal_size_max          0.373
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.294
_refine_diff_density_min         -0.406
_refine_diff_density_rms         0.053
_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     993
_refine_ls_number_reflns         14756
_refine_ls_number_restraints     1101
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0535
_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^)+(0.0755P)^2^+1.1299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1438
_refine_ls_wR_factor_ref         0.1544
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11931
_reflns_number_total             14756
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ae0c00811_si_002.cif
_cod_data_source_block           mba20006
_cod_original_cell_volume        3756.34(18)
_cod_database_code               4517875
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C87 H78 N4 O10'
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.583
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1-C1 \\sim Cl1A-C89
 with sigma of 0.02
 Cl2-C1 \\sim Cl2A-C89
 with sigma of 0.02
 Cl3-C1 \\sim Cl3A-C89
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl1A-Cl2A
 with sigma of 0.04
 Cl1-Cl3 \\sim Cl1A-Cl3A
 with sigma of 0.04
 Cl2-Cl3 \\sim Cl2A-Cl3A
 with sigma of 0.04
3. Rigid bond restraints
 Cl1, Cl2, Cl3, Cl3A, Cl1A, Cl2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17,
 C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33,
  C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48,
 C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64,
  C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78, C79,
 C80, C81, C82, C83, C84, C85, C86, C87, C88, C89, N7, N11, N27, N58, O4, O5,
 O6, O8, O9, O10, O12, O14, O18, O19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17,
 C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33,
  C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48,
 C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64,
  C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77, C78, C79,
 C80, C81, C82, C83, C84, C85, C86, C87, C88, C89, O4, O5, O6, O8, O9, O10, O12,
  O14, O18, O19, Cl1, Cl2, Cl3, Cl3A, Cl1A, Cl2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim Cl3 \\sim Cl3A \\sim Cl1A \\sim Cl2A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
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 C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim N7 \\sim N11 \\sim N27 \\sim N58 \\sim O4 \\sim O5 \\sim O6 \\sim O8
\\sim O9 \\sim O10 \\sim O12 \\sim O14 \\sim O18 \\sim O19: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
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 C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim O4 \\sim O5 \\sim O6 \\sim O8 \\sim O9 \\sim O10 \\sim O12 \\sim O14
\\sim O18 \\sim O19 \\sim Cl1 \\sim Cl2 \\sim Cl3 \\sim Cl3A \\sim Cl1A \\sim
Cl2A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 Cl3, C1, Cl1, Cl2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl3A, C89, Cl2A, Cl1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C89)=Sof(H89)=Sof(Cl3A)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C1)=Sof(H1)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C89(H89)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16),
 C19(H19), C20(H20), C21(H21), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
  C37(H37), C38(H38), C39(H39), C44(H44), C46(H46), C47(H47), C51(H51),
 C52(H52), C55(H55), C56(H56), C57(H57), C58(H58), C60(H60), C61(H61), C62(H62),
  C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C69(H69), C70(H70),
 C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C77(H77), C78(H78), C79(H79),
  C83(H83), C84(H84)
7.c Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C68(H68A,H68B,H68C), C76(H76A,H76B,
 H76C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C86(H86A,
 H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C)
;
_olex2_date_sample_data_collection 2020-01-21
_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 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.659