Long-lived charge separated states in spiro-compact rhodamine–naphthalenediimide D–A–D systems: synthesis and time-resolved optical and electron paramagnetic resonance spectroscopic studies
Tharmalingam, Balamurugan; Sukhanov, Andrey A.; Pei, Yuying; Sambucari, Greta; Ramos, Talita; Zhao, Jianzhang; Voronkova, Violeta K.; Di Donato, Mariangela; Physical Chemistry Chemical Physics  (2026) –; doi:10.1039/D5CP03836G

data_7251405
_publ_section_title
;
 Long-lived charge separated states in spiro-compact
 rhodamine--naphthalenediimide D--A--D systems: synthesis and
 time-resolved optical and electron paramagnetic resonance spectroscopic
 studies
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP03836G
_journal_year                    2026
_chemical_formula_moiety         'C70 H64 N8 O8'
_chemical_formula_sum            'C70 H64 N8 O8'
_chemical_formula_weight         1145.29
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-14
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2024-07-15 deposited with the CCDC.	2025-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.336(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.695(2)
_cell_length_b                   11.5619(18)
_cell_length_c                   18.283(3)
_cell_measurement_reflns_used    2879
_cell_measurement_temperature    126(2)
_cell_measurement_theta_max      20.28
_cell_measurement_theta_min      2.22
_cell_volume                     3183.8(8)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      126.0
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0923
_diffrn_reflns_av_unetI/netI     0.1132
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            22899
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.095
_diffrn_reflns_theta_max         25.095
_diffrn_reflns_theta_min         2.015
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5216
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1820 before and 0.0908 after correction. The Ratio of minimum to maximum transmission is 0.6999. The \l/2 correction factor is Not present.'
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_F_000             1208
_refine_diff_density_max         0.811
_refine_diff_density_min         -0.445
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         5621
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.1634
_refine_ls_R_factor_gt           0.0803
_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^)+(0.1373P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2179
_refine_ls_wR_factor_ref         0.2698
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2756
_reflns_number_total             5621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp03836g2.cif
_cod_data_source_block           1
_cod_database_code               7251405
_shelx_shelxl_version_number     2016/6
_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.a Secondary CH2 refined with riding coordinates:
 C010(H01A,H01B), C011(H01C,H01D), C012(H01E,H01F), C015(H01M,H01N)
2.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00I(H00I), C00M(H00M), C00P(H00P), C00Q(H00Q), C00R(H00R),
 C00S(H00S), C00T(H00T), C00U(H00U), C00V(H00V), C00Y(H00Y), C00Z(H00Z)
2.c Idealised Me refined as rotating group:
 C013(H01G,H01H,H01I), C014(H01J,H01K,H01L), C016(H01O,H01P,H01Q), C017(H01R,
 H01S,H01T)
;
_shelx_res_checksum              31456
_olex2_submission_special_instructions 'No special instructions were received'