Choosing Sides: Unusual Ultrafast Charge Transfer Pathways in an Asymmetric Electron-Accepting Cyclophane that Binds an Electron Donor
Zhou, Jiawang; Wu, Yilei; Roy, Indranil; Samanta, Avik; Stoddart, J. Fraser; Young, Ryan Michael; Wasielewski, Michael R.; Chemical Science  (2019) –; doi:10.1039/C8SC05514A

data_1550735
_publ_section_title
;
 Choosing Sides: Unusual Ultrafast Charge Transfer Pathways in an
 Asymmetric Electron-Accepting Cyclophane that Binds an Electron Donor
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC05514A
_journal_year                    2019
_chemical_formula_moiety
'4(F6 P), C46 H36 N6 S2, 2(C20 H12), 2(C2 H3 N)'
_chemical_formula_sum            'C90 H66 F24 N8 P4 S2'
_chemical_formula_weight         1903.50
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-19
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-10-09 deposited with the CCDC.    2019-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                101.538(10)
_cell_angle_beta                 95.067(11)
_cell_angle_gamma                104.449(10)
_cell_formula_units_Z            1
_cell_length_a                   10.448(2)
_cell_length_b                   10.636(2)
_cell_length_c                   19.123(4)
_cell_measurement_reflns_used    6861
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      64.591
_cell_measurement_theta_min      2.384
_cell_volume                     1994.7(7)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.978
_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  0.0675
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            16091
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        65.145
_diffrn_reflns_theta_max         65.145
_diffrn_reflns_theta_min         2.384
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    2.353
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.5931
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0817 before and 0.0409 after correction. The Ratio of minimum to maximum transmission is 0.7881. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_description       plate
_exptl_crystal_F_000             970
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.249
_exptl_crystal_size_mid          0.055
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     810
_refine_ls_number_reflns         6669
_refine_ls_number_restraints     887
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0961
_refine_ls_R_factor_gt           0.0760
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0465P)^2^+4.5400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1824
_refine_ls_wR_factor_ref         0.1943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5063
_reflns_number_total             6669
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05514a2.cif
_cod_data_source_block           cx1089
_cod_original_cell_volume        1994.8(7)
_cod_database_code               1550735
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.592
_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
 C1-H1B = C1-H1A
 0.99 with sigma of 0.02
 C1A-H1AB
 0.99 with sigma of 0.02
 H1AB-H1AA
 1.6 with sigma of 0.02
 N1-C8 \\sim N1AA_$1-C8A_$1 \\sim N4A_$1-C1A_$1 \\sim N4-C1
 with sigma of 0.001
 N2-C14 \\sim N2-C15 \\sim N3-C17 \\sim N3-C16
 with sigma of 0.001
 S2-C14 \\sim S2-C17 \\sim S1-C15 \\sim S1-C16
 with sigma of 0.001
 N0AA-C17 \\sim N3-C17 \\sim N3-C16 \\sim N1A-C16 \\sim N1A-C15 \\sim N2-C15
\\sim N2-C14
 with sigma of 0.01
 S2A-C14 \\sim S2A-C15 \\sim S1-C15 \\sim S1-C16 \\sim S3A-C16 \\sim S3A-C17
\\sim S2-C14 \\sim S2-C17
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(S2A)=Sof(N0AA)=Sof(N1A)=Sof(S3A)=0.5*(1-FVAR(2))
 Sof(S1)=Sof(S2)=Sof(N2)=Sof(N3)=0.5*FVAR(2)
 Fixed Sof: N1(0.5) N4(0.5) C16(0.5) C19(0.5) H19(0.5) C5(0.5) C4(0.5) H4(0.5)
 C3(0.5) H3(0.5) C2(0.5) C7(0.5) H7(0.5) C6(0.5) H6(0.5) C11(0.5) C22(0.5)
 H22(0.5) C10(0.5) H10(0.5) C14(0.5) C9(0.5) H9(0.5) C12(0.5) H12(0.5) C18(0.5)
 C20(0.5) H20(0.5) C13(0.5) H13(0.5) C15(0.5) C17(0.5) C8(0.5) H8A(0.5)
 H8B(0.5) C21(0.5) H21(0.5) C23(0.5) C28(0.5) H28(0.5) C27(0.5) H27(0.5)
 C26(0.5) C25(0.5) H25(0.5) C24(0.5) H24(0.5) C11A(0.5) C10A(0.5) H10A(0.5)
 C9A(0.5) H9A(0.5) N1AA(0.5) C13A(0.5) H13A(0.5) C12A(0.5) H12A(0.5) C8A(0.5)
 H8AA(0.5) H8AB(0.5) C5A(0.5) C4A(0.5) H4A(0.5) C3A(0.5) H3A(0.5) C2A(0.5)
 C7A(0.5) H7A(0.5) C6A(0.5) H6A(0.5) C18A(0.5) C22A(0.5) H22A(0.5) C21A(0.5)
 H21A(0.5) N4A(0.5) C20A(0.5) H20A(0.5) C19A(0.5) H19A(0.5) C1(0.5) C1A(0.5)
 H1A(0.5) H1B(0.5) H1AA(0.5) H1AB(0.5)
5.a Everything fixed:
 H1AA
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C8A(H8AA,H8AB)
5.c Aromatic/amide H refined with riding coordinates:
 C36(H36), C30(H30), C41(H41), C37(H37), C40(H40), C46(H46), C32(H32),
 C48(H48), C31(H31), C38(H38), C42(H42), C47(H47), C19(H19), C4(H4), C3(H3),
 C7(H7), C6(H6), C22(H22), C10(H10), C9(H9), C12(H12), C20(H20), C13(H13),
 C21(H21), C28(H28), C27(H27), C25(H25), C24(H24), C10A(H10A), C9A(H9A),
 C13A(H13A), C12A(H12A), C4A(H4A), C3A(H3A), C7A(H7A), C6A(H6A), C22A(H22A),
 C21A(H21A), C20A(H20A), C19A(H19A)
5.d Fitted hexagon refined as free rotating group:
 C5(C4,C3,C2,C7,C6), C23(C28,C27,C26,C25,C24), C11A(C10A,C9A,N1AA,C13A,C12A),
 C5A(C4A,C3A,C2A,C7A,C6A), C18A(C22A,C21A,N4A,C20A,C19A)
5.e Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C)
;
_shelx_res_checksum              55456
_olex2_date_sample_data_collection 2017-10-18
_olex2_date_sample_submission    2017-10-17
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1089
_olex2_submission_special_instructions 'No special instructions were received'