Conjugated Oligomers with Stable Radical Substituents: Synthesis, Single Crystal Structures, Electronic Structure, and Excited State Dynamics
Huang, Yiming; Xu, Zihao; Jin, Shijian; Li, Chenyang; Warncke, Kurt; Evangelista, Francesco A.; Lian, Tianquan; Egap, Eilaf; Chemistry of Materials 30 (2018) 7840–; doi:10.1021/acs.chemmater.8b03366

data_4003387
_publ_section_title
;
 Conjugated Oligomers with Stable Radical Substituents: Synthesis, Single
 Crystal Structures, Electronic Structure, and Excited State Dynamics
;
_journal_issue                   21
_journal_name_full               'Chemistry of Materials'
_journal_page_first              7840
_journal_paper_doi               10.1021/acs.chemmater.8b03366
_journal_volume                  30
_journal_year                    2018
_chemical_formula_moiety
'0.5(C50 H60 N4 O4 S6), 0.5(C50 H58 N4 O4 S6)'
_chemical_formula_sum            'C50 H59 N4 O4 S6'
_chemical_formula_weight         972.37
_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     dual
_audit_creation_date             2016-09-29
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2016.09.27 svn.r3342 for OlexSys, GUI svn.r5230)
;
_cell_angle_alpha                77.6816(15)
_cell_angle_beta                 88.6733(15)
_cell_angle_gamma                84.4995(15)
_cell_formula_units_Z            4
_cell_length_a                   11.9625(2)
_cell_length_b                   16.1003(3)
_cell_length_c                   27.6827(5)
_cell_measurement_reflns_used    31747
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.9950
_cell_measurement_theta_min      1.4920
_cell_volume                     5184.93(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'APEX2 v2014.11 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -11.76 196.24   0.50   30.00    --   28.00  73.80  54.24  416
  2  \w    -10.95 197.05   0.50   30.00    --   28.81  73.80 174.24  416
  3  \w    -10.95 197.05   0.50   30.00    --   28.81  73.80-105.76  416
  4  \w     38.55 197.05   0.50   30.00    --   28.81  73.80 134.24  317
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Bruker D8 diffractometer with APEX2 detector'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0411517000
_diffrn_orient_matrix_UB_12      -0.0279999000
_diffrn_orient_matrix_UB_13      0.0148941000
_diffrn_orient_matrix_UB_21      0.0316725000
_diffrn_orient_matrix_UB_22      0.0349023000
_diffrn_orient_matrix_UB_23      0.0003992000
_diffrn_orient_matrix_UB_31      -0.0291850000
_diffrn_orient_matrix_UB_32      0.0070009000
_diffrn_orient_matrix_UB_33      0.0215831000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0619
_diffrn_reflns_av_unetI/netI     0.0636
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            62999
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.682
_diffrn_reflns_theta_max         25.682
_diffrn_reflns_theta_min         1.506
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           35
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           45
_exptl_absorpt_coefficient_mu    0.310
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88879
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       plate
_exptl_crystal_F_000             2060
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.378
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.17
_refine_diff_density_max         1.599
_refine_diff_density_min         -1.086
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1166
_refine_ls_number_reflns         19603
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.1455
_refine_ls_R_factor_gt           0.1070
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1698P)^2^+19.5578P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2814
_refine_ls_wR_factor_ref         0.3105
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13201
_reflns_number_total             19603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm8b03366_si_003.cif
_cod_data_source_block           a634_sq
_cod_original_cell_volume        5184.91(17)
_cod_database_code               4003387
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.892
_reflns_odcompleteness_completeness 90.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.95
_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
 C73-C74
 1.522 with sigma of 0.02
 C25-C23 = C24-C22
 2.543 with sigma of 0.04
 C24-C23
 1.522 with sigma of 0.02
 C26-C25 = C25-C24 = C23-C22 = C22-C21
 1.52 with sigma of 0.002
 C26-C24 = C23-C21
 2.534 with sigma of 0.005
 C99-C98 = C98-C97
 1.52 with sigma of 0.001
 C95-C77
 1.52 with sigma of 0.001
 C96-C95 = C97-C96 = C98-C97 = C99-C98
 1.52 with sigma of 0.001
 C50-C49
 1.522 with sigma of 0.01
 C72-C74 = C73-C75
 2.543 with sigma of 0.04
 C100-C99
 1.52 with sigma of 0.004
 C71-C73 = C74-C76
 2.534 with sigma of 0.01
 C71-C72 = C72-C73 = C74-C75 = C75-C76
 1.52 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(C26) \\sim Ueq: with sigma of 0.007 and sigma for terminal atoms of 0.014
Uanis(C22) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C47) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C100) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C76) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C98) = Uanis(C99)
4. Rigid body (RIGU) restrains
 C21, C22, C23, C24, C25, C26
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C77, C95, C96, C97, C98, C99
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C45, C46, C47, C48, C49, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C99, C100
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C70, C71, C72, C73, C74, C75, C76
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B),
 C49(H49A,H49B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B),
  C99(H99A,H99B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C75(H75A,H75B)
5.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C28(H28), C41(H41),
 C42(H42), C43(H43), C44(H44), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69),
  C78(H78), C94(H94), C93(H93), C91(H91), C92(H92)
5.c Idealised Me refined with riding coordinates:
 C76(H76A,H76B,H76C)
5.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C26(H26A,H26B,H26C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C50(H50A,H50B,H50C), C61(H61A,H61B,H61C),
 C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C87(H87A,H87B,
 H87C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C),
 C100(H10A,H10B,H10C)
;
_shelx_fab_checksum              64154
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id RB4
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.110
_oxdiff_exptl_absorpt_empirical_full_min 0.893