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_7251406
_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         'C37 H36 N4 O4, C37 H35 N4 O4, C2 H3 N'
_chemical_formula_sum            'C76 H74 N9 O8'
_chemical_formula_weight         1241.44
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                86.872(6)
_cell_angle_beta                 87.845(5)
_cell_angle_gamma                83.021(6)
_cell_formula_units_Z            2
_cell_length_a                   12.294(2)
_cell_length_b                   13.387(2)
_cell_length_c                   20.532(3)
_cell_measurement_reflns_used    4345
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      23.41
_cell_measurement_theta_min      2.40
_cell_volume                     3347.5(9)
_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      150.0
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.978
_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  0.1182
_diffrn_reflns_av_unetI/netI     0.1028
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            43928
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        25.057
_diffrn_reflns_theta_max         25.057
_diffrn_reflns_theta_min         2.293
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6544
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1347 before and 0.0660 after correction.
The Ratio of minimum to maximum transmission is 0.8782.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_F_000             1314
_refine_diff_density_max         2.016
_refine_diff_density_min         -0.575
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     847
_refine_ls_number_reflns         11603
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.1762
_refine_ls_R_factor_gt           0.1104
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3114
_refine_ls_wR_factor_ref         0.3647
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6013
_reflns_number_total             11603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp03836g2.cif
_cod_data_source_block           1_CCDC1
_cod_original_cell_volume        3347.7(9)
_cod_database_code               7251406
_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:
 C00M(H00A,H00B), C00U(H00C,H00D), C01E(H01C,H01D), C01V(H01E,H01F), C01X(H01H,
 H01K), C01Y(H01N,H01O), C020(H02V,H02W), C029(H02D,H02E), C02D(H02G,H02H),
 C02G(H02I,H02J), C02J(H02N,H02O)
2.b Aromatic/amide H refined with riding coordinates:
 C00I(H00I), C00Q(H00Q), C00W(H00W), C00Y(H00Y), C014(H014), C017(H017),
 C01A(H01A), C01B(H01B), C01G(H01G), C01I(H01I), C01J(H01J), C01L(H01L),
 C01M(H01M), C01P(H01P), C01S(H01S), C01T(H01T), C01U(H01U), C01W(H01W),
 C01Z(H01Z), C022(H022), C024(H024), C025(H025), C026(H026), C02A(H02Z),
 C02B(H02F)
2.c Idealised Me refined as rotating group:
 C023(H02X,H02Y,H), C028(H02A,H02B,H02C), C02C(H02,HA,HB), C02E(H0AA,HC,HD),
 C02F(H2AA,HE,HF), C02H(H1AA,HG,HH), C02I(H02K,H02L,H02M), C02K(H02P,H02Q,H02R),
  C02L(H02S,H02T,H02U)
;
_shelx_res_checksum              63006
_olex2_submission_special_instructions 'No special instructions were received'