Impact of Methoxy Substituents on Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence in All-Organic Donor-Acceptor Systems.
Ward, Jonathan S.; Nobuyasu, Roberto S.; Fox, Mark A.; Aguilar, Juan A.; Hall, David; Batsanov, Andrei S.; Ren, Zhongjie; Dias, Fernando B.; Bryce, Martin R.; The Journal of organic chemistry 84 (2019) 3801–3816; doi:10.1021/acs.joc.8b02848

data_4034284
_publ_section_title
;
 Impact of Methoxy Substituents on Thermally Activated Delayed
 Fluorescence and Room-Temperature Phosphorescence in All-Organic
 Donor-Acceptor Systems.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              3801
_journal_page_last               3816
_journal_paper_doi               10.1021/acs.joc.8b02848
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C42 H34 N2 O4 S3, 1.6(C6 H5 Cl)'
_chemical_formula_sum            'C51.6 H42 Cl1.6 N2 O4 S3'
_chemical_formula_weight         906.97
_chemical_melting_point          622
_chemical_name_systematic
'Synthesis of 2,8-Bis(1,9-dimethyl-3-methoxyphenothiazin-10-yl)dibenzothiophene-S,S-dioxide'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-09-06
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 112.4493(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.3637(6)
_cell_length_b                   14.6487(5)
_cell_length_c                   28.5013(9)
_cell_measurement_reflns_used    9899
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      65.24
_cell_measurement_theta_min      3.356
_cell_volume                     9015.3(5)
_computing_cell_refinement       'SAINT v8.38A (Bruker, 2016)'
_computing_data_collection       'APEX3 v.2016.1-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
'ShelXL 2018/3 multi-CPU version (Sheldrick, 2015a)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'Bruker PHOTON 100 CMOS'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device       '3-circle area detector diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1057
_diffrn_reflns_av_unetI/netI     0.0800
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            93916
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         66.710
_diffrn_reflns_theta_min         3.102
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\mS microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.762
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; SADABS-2016/2 (Krause et al., 2015) was used for absorption correction. 
 wR2(int) was 0.1163 before and 0.0639 after correction. The Ratio of 
 minimum to maximum transmission is 0.8304. The \l/2 correction factor 
 is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.336
_exptl_crystal_description       prism
_exptl_crystal_F_000             3782
_exptl_crystal_size_max          0.414
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.754
_refine_diff_density_min         -0.454
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1222
_refine_ls_number_reflns         15593
_refine_ls_number_restraints     960
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.1342
_refine_ls_R_factor_gt           0.0725
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0874P)^2^+15.2413P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1728
_refine_ls_wR_factor_ref         0.2042
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9163
_reflns_number_total             15593
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02848_si_002.cif
_cod_data_source_block           3b_17s311
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4034284
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.394
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C39-C28 = C39B-C28B
 1.5 with sigma of 0.02
 O3B'-C43'
 1.4 with sigma of 0.02
 C7S-C8S \\sim C9S-C8S \\sim C9S_$1-C7S
 with sigma of 0.02
 C26-C21 \\sim C26B-C21B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C1SA) = Uiso(C6S)
Uiso(C2SA) = Uiso(C2S)
Uiso(C3S) = Uiso(C3SA)
Uiso(C5S) = Uiso(C6SA)
Uanis(C9S) = Uanis(C8S) = Uanis(C7S)
Uiso(C2T) = Uiso(C3TA)
Uiso(C6TB) = Uiso(C5TB) = Uiso(C4TB) = Uiso(C3TB) = Uiso(C2TB)
Uiso(C6T) = Uiso(C1A)
4. 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
5. Others
 Fixed Sof: H16(0.2) H37(0.2) O4(0.8) O5(0.8) C21(0.8) C22(0.8) H22(0.8)
 C23(0.8) H23(0.8) C24(0.8) H24(0.8) C26(0.8) H26A(0.8) H26B(0.8) H26C(0.8)
 C27(0.8) C28(0.8) C29(0.8) H29(0.8) C30(0.8) H30(0.8) C31(0.8) H31(0.8)
 C32(0.8) C39(0.5) H39A(0.5) H39B(0.5) H39C(0.5) C42(0.8) H42A(0.8) H42B(0.8)
 H42C(0.8) C43(0.8) H43A(0.8) H43B(0.8) H43C(0.8) O4B(0.2) C27B(0.2) C28B(0.2)
 C29B(0.2) H29B(0.2) C30B(0.2) C31B(0.2) H31B(0.2) C32B(0.2) C39B(0.5)
 H39D(0.5) H39E(0.5) H39F(0.5) C42B(0.2) H42D(0.2) H42E(0.2) H42F(0.2) O3B(0.2)
 C21B(0.2) C22B(0.2) H22B(0.2) C23B(0.2) C24B(0.2) H24B(0.2) C26B(0.2)
 H26D(0.2) H26E(0.2) H26F(0.2) C41B(0.2) H41A(0.2) H41B(0.2) H41C(0.2)
 O3'(0.63) O4B'(0.42) H16'(0.63) H23'(0.37) H30'(0.58) H37'(0.42) C41'(0.63)
 H41D(0.63) H41E(0.63) H41F(0.63) C44'(0.42) H44A(0.42) H44B(0.42) H44C(0.42)
 O3B'(0.37) C43'(0.37) H43D(0.37) H43E(0.37) H43F(0.37) O4'(0.58) C42'(0.58)
 H42G(0.58) H42H(0.58) H42I(0.58) Cl2(0.5) C1T(0.5) C2T(0.5) H2T(0.5) C3T(0.5)
 H3T(0.5) C4T(0.5) H4T(0.5) C5T(0.5) H5T(0.5) C6T(0.5) H6T(0.5) Cl2A(0.38)
 C1TA(0.38) C1A(0.38) H1A(0.38) C5TA(0.38) H5TA(0.38) C4TA(0.38) H4TA(0.38)
 C3TA(0.38) H3TA(0.38) C2TA(0.38) H2TA(0.38) Cl2B(0.12) C1TB(0.12) C6TB(0.12)
 H6TB(0.12) C5TB(0.12) H5TB(0.12) C4TB(0.12) H4TB(0.12) C3TB(0.12) H3TB(0.12)
 C2TB(0.12) H2TB(0.12) Cl1(0.48) C1S(0.6) C6S(0.6) H6S(0.6) C5S(0.6) H5S(0.6)
 C4S(0.6) H4S(0.6) C3S(0.6) H3S(0.6) C2S(0.6) H2S(0.6) Cl1A(0.4) C1SA(0.4)
 C6SA(0.4) H6SA(0.4) C5SA(0.4) H5SA(0.4) C4SA(0.4) H4SA(0.4) C3SA(0.4)
 H3SA(0.4) C2SA(0.4) H2SA(0.4) Cl1B(0.12) Cl4(0.2) C7S(0.4) C9S(0.4) H9S(0.4)
 C8S(0.4) H8S(0.4)
6.a Riding coordinates:
 C16(H16), C39B(H39D,H39E,H39F), C16'(H16'), C37'(H37'), C41'(H41D,H41E,H41F),
 C44'(H44A,H44B,H44C), C43'(H43D,H43E,H43F)
6.b Me refined with riding coordinates:
 C26B(H26D,H26E,H26F), C41B(H41A,H41B,H41C)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C8(H8), C10(H10), C11(H11), C15(H15), C17(H17),
 C36(H36), C37(H37), C38(H38), C22(H22), C23(H23), C24(H24), C29(H29), C30(H30),
  C31(H31), C29B(H29B), C31B(H31B), C22B(H22B), C24B(H24B), C2'(H2'), C3'(H3'),
 C5'(H5'), C8'(H8'), C10'(H10'), C11'(H11'), C15'(H15'), C17'(H17'), C22'(H22'),
  C23'(H23'), C24'(H24'), C29'(H29'), C30'(H30'), C31'(H31'), C36'(H36'),
 C38'(H38'), C2T(H2T), C3T(H3T), C4T(H4T), C5T(H5T), C6T(H6T), C1A(H1A),
 C5TA(H5TA), C4TA(H4TA), C3TA(H3TA), C2TA(H2TA), C6TB(H6TB), C5TB(H5TB),
 C4TB(H4TB), C3TB(H3TB), C2TB(H2TB), C6S(H6S), C5S(H5S), C4S(H4S), C3S(H3S),
 C2S(H2S), C6SA(H6SA), C5SA(H5SA), C4SA(H4SA), C3SA(H3SA), C2SA(H2SA),
 C12S(H12S), C16S(H16S), C15S(H15S), C13S(H13S), C14S(H14S), C9S(H9S), C8S(H8S)
6.d Fitted hexagon refined as free rotating group:
 C1T(C2T,C3T,C4T,C5T,C6T), C1TA(C1A,C5TA,C4TA,C3TA,C2TA), C1TB(C6TB,C5TB,C4TB,
 C3TB,C2TB), C1S(C6S,C5S,C4S,C3S,C2S), C1SA(C6SA,C5SA,C4SA,C3SA,C2SA)
6.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C40(H40A,H40B,H40C), C26(H26A,H26B,H26C), C39(H39A,H39B,
 H39C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C42B(H42D,H42E,H42F),
 C25'(H25D,H25E,H25F), C26'(H26G,H26H,H26I), C39'(H39G,H39H,H39I), C40'(H40D,
 H40E,H40F), C42'(H42G,H42H,H42I)
;
_shelx_res_checksum              76997
_shelx_hkl_checksum              59528
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'