Modulation of Charge Transfer by N-Alkylation to Control Photoluminescence Energy and Quantum Yield
Turley, Andrew; Danos, Andrew; Prlj, Antonio; Monkman, Andrew P.; Curchod, Basile; McGonigal, Paul R.; Etherington, Marc Kenneth; Chemical Science  (2020) –; doi:10.1039/D0SC02460K

data_1558274
_publ_section_title
;
 Modulation of Charge Transfer by N-Alkylation to Control
 Photoluminescence Energy and Quantum Yield
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02460K
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'B F4, C21 H27 N2 O2, 0.5(H2 O)'
_chemical_formula_sum            'C21 H28 B F4 N2 O2.5'
_chemical_formula_weight         435.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-08-05
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_audit_update_record
;
2020-02-24 deposited with the CCDC.	2020-06-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.2832(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0721(2)
_cell_length_b                   15.6353(5)
_cell_length_c                   16.4422(5)
_cell_measurement_reflns_used    9656
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      74.25
_cell_measurement_theta_min      2.72
_cell_volume                     2053.52(10)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS, 2016)'
_computing_data_collection       'APEX2 v.2013.4_1 (Bruker, 2013)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS, 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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'Bruker PHOTON 100 CMOS'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS sensor'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       '3-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'focusing mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            23769
_diffrn_reflns_point_group_measured_fraction_full 0.902
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.988
_diffrn_reflns_theta_min         2.716
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms microsource'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.983
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0898 before and 0.0443 after correction. 
The Ratio of minimum to maximum transmission is 0.8637. 
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       plank
_exptl_crystal_F_000             916
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.647
_refine_diff_density_min         -0.589
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 2602 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     575
_refine_ls_number_reflns         6963
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0424
_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^)+(0.0400P)^2^+1.6700P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0996
_refine_ls_wR_factor_ref         0.1050
_reflns_Friedel_coverage         0.738
_reflns_Friedel_fraction_full    0.804
_reflns_Friedel_fraction_max     0.790
_reflns_number_gt                6575
_reflns_number_total             6963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02460k2.cif
_cod_data_source_block           MeQn_17srv201
_cod_original_formula_sum        'C21 H28 B F4 N2 O2.50'
_cod_database_code               1558274
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.683
_computing.bruker_data_scaling   'SADABS V2012/1 (Bruker AXS Inc.)'
_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
 C8B-C7A \\sim C8A-C7A
 with sigma of 0.002
 C9A-C8A \\sim C9B-C8B
 with sigma of 0.002
 N1A-C10B \\sim N1A-C10A
 with sigma of 0.002
 C8A-C7A \\sim C8B-C7B
 with sigma of 0.002
 C7B-C6B \\sim C7A-C6A
 with sigma of 0.002
 C7A-C3A \\sim C7B-C3A
 with sigma of 0.002
 N1A-C6A \\sim N1A-C6B
 with sigma of 0.002
 O1A-H1A \\sim O1W-H1WB \\sim O1W-H1WA \\sim O1-H1
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uiso(C7B) = Uiso(C7A)
4. Others
 Fixed Sof: H3A(0.6) H3AA(0.4) C6A(0.6) H6AA(0.6) H6AB(0.6) C6B(0.4) H6BA(0.4)
 H6BB(0.4) C7A(0.6) H7A(0.6) C7B(0.4) H7B(0.4) C8A(0.6) H8A(0.6) C8B(0.4)
 H8B(0.4) C9A(0.6) H9AA(0.6) H9AB(0.6) C9B(0.4) H9BA(0.4) H9BB(0.4) C10A(0.4)
 H10A(0.4) H10B(0.4) H10C(0.4) C10B(0.6) H10D(0.6) H10E(0.6) H10F(0.6)
5.a Ternary CH refined with riding coordinates:
 C1(H1B), C3(H3), C7(H7), C11(H11), C1A(H1AA), C3A(H3A), C3A(H3AA), C7A(H7A),
 C7B(H7B), C11A(H11A)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C2A(H2AA,H2AB), C4A(H4AA,
 H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB), C6B(H6BA,H6BB)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C13(H13), C14(H14), C16(H16), C17(H17), C19(H19), C8A(H8A), C8B(H8B),
 C13A(H13A), C14A(H14A), C16A(H16A), C17A(H17A), C19A(H19A)
5.d X=CH2 refined with riding coordinates:
 C9(H9A,H9B), C9A(H9AA,H9AB), C9B(H9BA,H9BB)
5.e Idealised Me refined as rotating group:
 C10(H10G,H10H,H10I), C21(H21D,H21E,H21F), C10A(H10A,H10B,H10C), C10B(H10D,
 H10E,H10F), C21A(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'