Davydov splitting and singlet fission in excitonically coupled pentacene dimers
Basel, Bettina Sabine; Hetzer, Constantin; Zirzlmeier, Johannes; Thiel, Dominik; Guldi, Rebecca; Hampel, Frank; Kahnt, Axel; Clark, Timothy; Guldi, Dirk Michael; Tykwinski, Rik R.; Chemical Science  (2019) –; doi:10.1039/C9SC00384C

data_1550721
_publ_section_title
;
 Davydov splitting and singlet fission in excitonically coupled pentacene
 dimers
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC00384C
_journal_year                    2019
_chemical_formula_moiety         'C99 H106 O Si2'
_chemical_formula_sum            'C99 H106 O Si2'
_chemical_formula_weight         1368.01
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-04-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_audit_update_record
;
2018-04-26 deposited with the CCDC.    2019-02-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.9069(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.8126(4)
_cell_length_b                   18.0121(3)
_cell_length_c                   38.6964(5)
_cell_measurement_reflns_used    11502
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      60.5290
_cell_measurement_theta_min      3.9750
_cell_volume                     17130.0(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      173.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6144
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.806
_diffrn_measured_fraction_theta_max 0.965
_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    -39.00  25.00   1.00   68.17    --    0.00  95.00-132.00   64
  2  \w     13.00  98.00   1.00  272.69    --   80.57 -45.00 150.00   85
  3  \w      7.00 106.00   1.00  272.69    --   80.57 -94.00 -60.00   99
  4  \w     80.00 141.00   1.00  272.69    --   80.57  45.00 -30.00   61
  5  \w     54.00  87.00   1.00  272.69    --   80.57  77.00   0.00   33
  6  \w     42.00 111.00   1.00  272.69    --   80.57 -77.00  60.00   69
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0278511000
_diffrn_orient_matrix_UB_12      0.0178520000
_diffrn_orient_matrix_UB_13      0.0371633000
_diffrn_orient_matrix_UB_21      -0.0178553000
_diffrn_orient_matrix_UB_22      0.0816516000
_diffrn_orient_matrix_UB_23      -0.0049151000
_diffrn_orient_matrix_UB_31      -0.0532732000
_diffrn_orient_matrix_UB_32      -0.0179677000
_diffrn_orient_matrix_UB_33      0.0145248000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.806
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            22628
_diffrn_reflns_point_group_measured_fraction_full 0.806
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         60.580
_diffrn_reflns_theta_min         3.340
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.710
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_description       block
_exptl_crystal_F_000             5888
_exptl_crystal_recrystallization_method 'crystallized from CHCl2/Acetone'
_exptl_crystal_size_max          0.102
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.623
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     943
_refine_ls_number_reflns         12510
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.228
_refine_ls_R_factor_all          0.0786
_refine_ls_R_factor_gt           0.0703
_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^)+(0.1163P)^2^+27.8145P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1945
_refine_ls_wR_factor_ref         0.2028
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10631
_reflns_number_total             12510
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc00384c2.cif
_cod_data_source_block           16tyk_ch01_2
_cod_original_cell_volume        17130.1(5)
_cod_database_code               1550721
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C80 H60 O Si2'
_reflns_odcompleteness_completeness 98.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     58.03
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 Si2-C107 \\sim Si2A-C108
 with sigma of 0.02
 Si2-C11A \\sim Si2A-C111
 with sigma of 0.02
 Si2A-C107 \\sim Si2-C107 \\sim Si2-C11A \\sim Si2A-C111 \\sim Si2A-C103 \\sim
Si2-C103
 with sigma of 0.02
 C27A-C25 \\sim C28-C25 \\sim C25-C26A \\sim C27-C25 \\sim C28A-C25 \\sim
C26-C25
 with sigma of 0.02
 C64A-C63 \\sim C64-C63
 with sigma of 0.02
 C64A-C65 \\sim C65-C64 \\sim C64A-C66 \\sim C66-C64
 with sigma of 0.02
 C112-C111 \\sim C112-C11A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Si2) = Uanis(Si2A)
Uanis(C107) = Uanis(C108)
Uanis(C111) = Uanis(C11A)
Uanis(C27) = Uanis(C28A) = Uanis(C26) = Uanis(C27A) = Uanis(C28) = Uanis(C26A)
Uanis(C64A) = Uanis(C64)
4. Others
 Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(H27D)=Sof(H27E)=
 Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(H63C)=Sof(H63D)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(H66D)=Sof(H66E)=
 Sof(H66F)=Sof(C64A)=Sof(H64A)=1-FVAR(2)
 Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=FVAR(2)
 Sof(H10C)=Sof(H10D)=Sof(H10M)=Sof(H10N)=Sof(H11H)=Sof(Si2A)=Sof(C111)=
 Sof(H11F)=Sof(H11G)=1-FVAR(3)
 Sof(Si2)=Sof(C11A)=Sof(H11A)=Sof(H11B)=Sof(H10A)=Sof(H10B)=Sof(H10K)=
 Sof(H10L)=Sof(H112)=FVAR(3)
5.a Riding coordinates:
 C65(H65A,H65B,H65C), C65(H65D,H65E,H65F), C66(H66A,H66B,H66C), C66(H66D,H66E,
 H66F), C112(H112), C112(H11H)
5.b Ternary CH refined with riding coordinates:
 C64(H64), C68(H68), C72(H72), C104(H104), C108(H108), C64A(H64A)
5.c Secondary CH2 refined with riding coordinates:
 C11A(H11A,H11B), C63(H63A,H63B), C63(H63C,H63D), C67(H67A,H67B), C71(H71A,
 H71B), C103(H10A,H10B), C103(H10C,H10D), C107(H10K,H10L), C107(H10M,H10N),
 C111(H11F,H11G)
5.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C16(H16), C20(H20), C22(H22), C43(H43), C45(H45), C46(H46),
 C47(H47), C48(H48), C50(H50), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
  C61(H61), C83(H83), C85(H85), C86(H86), C87(H87), C88(H88), C90(H90),
 C94(H94), C96(H96), C97(H97), C98(H98), C99(H99), C101(H101)
5.e Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C73(H73A,H73B,H73C),
 C74(H74A,H74B,H74C), C105(H10E,H10F,H10G), C106(H10H,H10I,H10J), C109(H10O,
 H10P,H10Q), C110(H11C,H11D,H11E), C113(H11I,H11J,H11K), C114(H11L,H11M,H11N),
 C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F)
;
_olex2_date_sample_data_collection 2016-06-02
_olex2_date_sample_submission    2016-05-05
_olex2_exptl_crystal_mounting_method 'mounted on a loop'
_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 1.436
_oxdiff_exptl_absorpt_empirical_full_min 0.780