Spiro-Based Thermally Activated Delayed Fluorescence Emitters with Reduced Nonradiative Decay for High-Quantum-Efficiency, Low-Roll-Off, Organic Light-Emitting Diodes.
Sharma, Nidhi; Maciejczyk, Michal; Hall, David; Li, Wenbo; Liégeois, Vincent; Beljonne, David; Olivier, Yoann; Robertson, Neil; Samuel, Ifor D. W.; Zysman-Colman, Eli; ACS applied materials & interfaces 13 (2021) 44628–44640; doi:10.1021/acsami.1c12234

data_4519039
_publ_section_title
;
 Spiro-Based Thermally Activated Delayed Fluorescence Emitters with
 Reduced Nonradiative Decay for High-Quantum-Efficiency, Low-Roll-Off,
 Organic Light-Emitting Diodes.
;
_journal_issue                   37
_journal_name_full               'ACS applied materials &amp; interfaces'
_journal_page_first              44628
_journal_page_last               44640
_journal_paper_doi               10.1021/acsami.1c12234
_journal_volume                  13
_journal_year                    2021
_chemical_formula_moiety         '2(C H2 Cl2), C77 H60 N2 O3 P2, 2(C H4 O)'
_chemical_formula_sum            'C81 H72 Cl4 N2 O5 P2'
_chemical_formula_weight         1357.14
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-11-15
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.619(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   32.3093(8)
_cell_length_b                   8.91065(19)
_cell_length_c                   24.5282(6)
_cell_measurement_reflns_used    24201
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      29.0820
_cell_measurement_theta_min      3.1700
_cell_volume                     6981.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.912
_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    -88.00  27.00   1.00   15.00    --   -9.43 -19.00 120.00  115
  2  \w    -76.00 -33.00   1.00   15.00    --   -9.43 143.00 -18.12   43
  3  \w    -20.00  30.00   1.00   15.00    --   -9.43 -99.00  30.00   50
  4  \w    -20.00  30.00   1.00   15.00    --   -9.43 -99.00  60.00   50
  5  \w    -84.00 -38.00   1.00   15.00    --   -9.43 153.00-111.09   46
  6  \w    -32.00  63.00   1.00   15.00    --   -9.43  38.00 120.00   95
  7  \w    -20.00  30.00   1.00   15.00    --   -9.43 -99.00-180.00   50
  8  \w    -88.00  27.00   1.00   15.00    --   -9.43 -19.00  30.00  115
  9  \w      0.00  26.00   1.00   15.00    --   -9.43 -99.00  90.00   26
 10  \w    -55.00 -28.00   1.00   15.00    --   10.84 -38.00  90.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0199936000
_diffrn_orient_matrix_UB_12      0.0158849000
_diffrn_orient_matrix_UB_13      0.0072458000
_diffrn_orient_matrix_UB_21      0.0080472000
_diffrn_orient_matrix_UB_22      -0.0118635000
_diffrn_orient_matrix_UB_23      0.0281909000
_diffrn_orient_matrix_UB_31      0.0053596000
_diffrn_orient_matrix_UB_32      0.0770765000
_diffrn_orient_matrix_UB_33      0.0028542000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0505
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.912
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            60686
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.585
_diffrn_reflns_theta_min         2.962
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.270
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.675
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       block
_exptl_crystal_F_000             2840
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of methanol and dichloromethane by solvent layering'
_exptl_crystal_size_max          0.505
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.099
_refine_diff_density_max         0.571
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     450
_refine_ls_number_reflns         8947
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0709
_refine_ls_R_factor_gt           0.0556
_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^)+(0.0471P)^2^+15.4449P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1283
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7341
_reflns_number_total             8947
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            am1c12234_si_003.cif
_cod_data_source_block           nr17027
_cod_database_code               4519039
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C77 H60 N2 O3 P2'
_chemical_oxdiff_usercomment     '@ 120 K M82'
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O3-H3A
 0.84 with sigma of 0.02
 Cl2-Cl1 \\sim Cl1A-Cl2A
 with sigma of 0.04
 C40-Cl2 \\sim C40-Cl1 \\sim C40-Cl1A \\sim C40-Cl2A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 Cl1, Cl2, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1A, Cl2A, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(H40C)=Sof(H40D)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(H40A)=Sof(H40B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C40(H40A,H40B), C40(H40C,H40D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C12(H12), C13(H13), C16(H16),
 C17(H17), C19(H19), C20(H20), C23(H23), C25(H25), C26(H26), C29(H29), C30(H30),
  C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              11746
_shelx_hkl_checksum              24202
_olex2_date_sample_data_collection 2017-11-14
_olex2_date_sample_submission    2017-11-10
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id SFX-POMeDPA
_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 1.333
_oxdiff_exptl_absorpt_empirical_full_min 0.700