An order of magnitude modulation of singlet fission rates in NDI cyclophanes by tuning inter-chromophoric electronic coupling.
Mohanty, Aisworika; Singh, Vijay Pal; Hussain, Ch Mudasar; Dey, Mandira; Ghosh, Debashree; Mukhopadhyay, Pritam; Dasgupta, Jyotishman; Chemical science 16 (2025) 21368–21378; doi:10.1039/d5sc05995j

data_1576051
_publ_section_title
;
 An order of magnitude modulation of singlet fission rates in NDI
 cyclophanes by tuning inter-chromophoric electronic coupling.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              21368
_journal_page_last               21378
_journal_paper_doi               10.1039/d5sc05995j
_journal_volume                  16
_journal_year                    2025
_chemical_compound_source        synthesised
_chemical_formula_moiety         '0.039(C60 H58 N8 O8)'
_chemical_formula_sum            'C H N O'
_chemical_formula_weight         43.03
_chemical_melting_point          'above 573 K'
_chemical_name_common            'Meta-Meta macrocycle'
_chemical_name_systematic        'Meta-Meta dimer'
_chemical_properties_physical    Light-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-12-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-02-18 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.087(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.4576(11)
_cell_length_b                   21.8026(17)
_cell_length_c                   15.2057(12)
_cell_measurement_reflns_used    9877
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      27.955
_cell_measurement_theta_min      2.297
_cell_volume                     5124.6(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1469
_diffrn_reflns_av_unetI/netI     0.1764
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            99601
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.430
_diffrn_reflns_theta_min         2.097
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.128
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6058
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1438 before and 0.0751 after correction.
The Ratio of minimum to maximum transmission is 0.8124.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       rectangular
_exptl_crystal_F_000             2244
_exptl_crystal_recrystallization_method 'layring of toluene on chcloroform'
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 3185 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.5(6)
_refine_ls_extinction_coef       0.00031(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1378
_refine_ls_number_reflns         25378
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.2715
_refine_ls_R_factor_gt           0.1396
_refine_ls_shift/su_max          1.456
_refine_ls_shift/su_mean         0.006
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0391P)^2^+12.5844P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2141
_refine_ls_wR_factor_ref         0.2640
_reflns_Friedel_coverage         0.985
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                11174
_reflns_number_total             25378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05995j2.cif
_cod_data_source_block           om_0ma_a
_cod_depositor_comments
'Adding full bibliography for 1576051--1576052.cif.'
_cod_database_code               1576051
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C01O(H01a,H01b), C027(H02a,H02b), C028(H02i,H02k), C02A(H02c,H02d), C02H(H02e,
 H02f), C02M(H02g,H02h), C02Y(H02o,H02p), C037(H03a,H03b), C03A(H03c,H03d),
 C03D(H03v,H03w), C03F(H03x,H03y), C03G(H03z,H), C03H(H03,Ha), C03I(H03f,H03g),
 C03J(H03h,H03i), C03K(H3,Hb), C03L(H03j,H03k), C03M(H03l,H03m), C03N(H03n,
 H03o), C03O(H6,Hc), C03P(H7,Hd), C03Q(H8,He), C03U(H9,Hf), C03V(H10,Hg),
 C5(H5a,H5b), C040(H04d,H04e), C7(H7a,H7b), C8(H8a,H8b)
2.b Aromatic/amide H refined with riding coordinates:
 N00E(H00E), N00F(H00F), N00H(H00H), C2(H2), N00P(H00P), N5(H5), N1(H1),
 N2(H2a), C01M(H01M), N4(H4), C01U(H01U), C01V(H01V), C01Y(H01Y), C023(H023),
 C02D(H02l), C02J(H02J), C02L(H02m), C02N(H02N), C02R(H02R), C02S(H02S),
 C02U(H02U), C02V(H02V), C02X(H02X), C030(H030), C031(H031), C035(H035),
 C036(H036), C038(H038), C039(H039), C12(H12), C03C(H03u), C03E(H03E),
 C03R(H03R), C03T(H03T), C03X(H13), C042(H042)
2.c Idealised Me refined as rotating group:
 C03W(H11,Hh,Hi), C03Y(H03p,H03q,H03s), C041(H04f,H04g,H04h), C043(H04a,H04b,
 H04c), C6(H6a,H6b,H6c), C9(H9a,H9b,H9c), C10(H10a,H10b,H10c), C11(H11a,H11b,
 H11c)
;
_shelx_res_checksum              33152
_olex2_submission_special_instructions 'No special instructions were received'