Charge-Transfer Biexciton Annihilation in a Donor-Acceptor Co-crystal yields High-Energy Long-Lived Charge Carriers
Wasielewski, Michael R.; Schlesinger, Itai; Powers-Riggs, Natalia E; Logsdon, Jenna L.; Qi, Yue; Miller, Stephen A.; Tempelaar, Roel; Young, Ryan Michael; Chemical Science  (2020) –; doi:10.1039/D0SC03301D

data_1558850
_publ_section_title
;
 Charge-Transfer Biexciton Annihilation in a Donor-Acceptor Co-crystal
 yields High-Energy Long-Lived Charge Carriers
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03301D
_journal_year                    2020
_chemical_formula_moiety         'C58 H50 N2 O4, 2(C10 H5.5 O)'
_chemical_formula_sum            'C78 H56 N2 O6'
_chemical_formula_weight         1117.24
_chemical_name_systematic        Ph4PDI_PXX
_space_group_crystal_system      orthorhombic
_space_group_IT_number           71
_space_group_name_Hall           '-I 2 2'
_space_group_name_H-M_alt        'I m m m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-03-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-21 deposited with the CCDC.	2020-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.9513(19)
_cell_length_b                   20.343(7)
_cell_length_c                   22.590(6)
_cell_measurement_reflns_used    1725
_cell_measurement_temperature    100
_cell_measurement_theta_max      58.83
_cell_measurement_theta_min      2.923
_cell_volume                     3194.5(16)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'Bruker SAINT'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.1
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.942
_diffrn_measured_fraction_theta_max 0.942
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0310
_diffrn_reflns_av_unetI/netI     0.0300
_diffrn_reflns_Laue_measured_fraction_full 0.942
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            5237
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        59.316
_diffrn_reflns_theta_max         59.316
_diffrn_reflns_theta_min         2.923
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    0.577
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.5932
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0774 before and 0.0463 after correction. The Ratio of minimum to maximum transmission is 0.7892. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.162
_exptl_crystal_description       plate
_exptl_crystal_F_000             1172
_exptl_crystal_preparation
'Equal ratio of Ph4PDI and PXX measured and disolved in toluene.'
_exptl_crystal_recrystallization_method
'Crystals were grown through slow diffusion of methanol into a toluene solution.'
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.451
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.881
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     185
_refine_ls_number_reflns         1273
_refine_ls_number_restraints     363
_refine_ls_restrained_S_all      1.762
_refine_ls_R_factor_all          0.1380
_refine_ls_R_factor_gt           0.1087
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3982
_refine_ls_wR_factor_ref         0.4373
_reflns_Friedel_coverage         0.000
_reflns_number_gt                880
_reflns_number_total             1273
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03301d2.cif
_cod_data_source_block           ph4pdipxx_ortho_cs
_cod_original_cell_volume        3194.4(16)
_cod_database_code               1558850
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C10A_$1-C10A
 2.1 with sigma of 0.02
 C9A_$1-C9A
 2.4 with sigma of 0.02
 O2-C25 \\sim O2-C15 \\sim O3-C22 \\sim O3-C28
 with sigma of 0.01
3. Restrained planarity
 O2, O3, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28,
 C29, C30, C31, C32, C33, C34
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C33) = Uanis(O2) = Uanis(C25) = Uanis(C15) = Uanis(C34) = Uanis(C26) =
Uanis(C16) = Uanis(C24) = Uanis(C27) = Uanis(C23) = Uanis(C17) = Uanis(C19) =
Uanis(C32) = Uanis(C28) = Uanis(C22) = Uanis(C18) = Uanis(C20) = Uanis(C31) =
Uanis(C29) = Uanis(O3) = Uanis(C21) = Uanis(C30)
5. 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
6. Others
 Sof(C9)=Sof(HA)=Sof(C10)=Sof(HC)=Sof(HF)=1-FVAR(1)
 Sof(C9A)=Sof(HB)=Sof(C10A)=Sof(HD)=Sof(HE)=FVAR(1)
 Sof(HJ)=Sof(HK)=Sof(C14A)=Sof(HO)=Sof(HP)=Sof(HQ)=0.5*(1-FVAR(3))
 Sof(HH)=Sof(HI)=Sof(C14)=Sof(HL)=Sof(HM)=Sof(HN)=0.5*FVAR(3)
 Fixed Sof: HG(0.25) O2(0.125) O3(0.125) C15(0.125) C16(0.125) H16(0.125)
 C17(0.125) C18(0.125) H18(0.125) C19(0.125) C20(0.125) H20(0.125) C21(0.125)
 H21(0.125) C22(0.125) C23(0.125) C24(0.125) C28(0.125) C29(0.125) H29(0.125)
 C30(0.125) H30(0.125) C31(0.125) H31(0.125) C34(0.125) H34(0.125) C33(0.125)
 H33(0.125) C32(0.125) C27(0.125) C26(0.125) C25(0.125)
7.a Ternary CH refined with riding coordinates:
 C12(HG)
7.b Secondary CH2 refined with riding coordinates:
 C13(HH,HI), C13(HJ,HK)
7.c Aromatic/amide H refined with riding coordinates:
 C4(H), C9(HA), C9A(HB), C10(HC), C10A(HD), C11(HE), C11(HF), C16(H16),
 C18(H18), C20(H20), C21(H21), C29(H29), C30(H30), C31(H31), C34(H34), C33(H33)
7.d Fitted hexagon refined as free rotating group:
 C34(C33,C32,C27,C26,C25)
7.e Idealised Me refined as rotating group:
 C14(HL,HM,HN), C14A(HO,HP,HQ)
;
_olex2_exptl_crystal_mounting_method
'Appropriate crystal was selected and affixed to a loop with paratone oil.'
_olex2_submission_special_instructions 'No special instructions were received'