Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro.
Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Savoie, Huguette; Flanagan, Keith J.; Sy, Cindy; Sitte, Elisabeth; Telitchko, Maxime; Laquai, Frédéric; Boyle, Ross W.; Senge, Mathias O.; Journal of the American Chemical Society 139 (2017) 6282–6285; doi:10.1021/jacs.7b00551

data_4126186
_publ_section_title
;
 Generation of Triplet Excited States via Photoinduced Electron Transfer
 in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in
 Solution and in Vitro.
;
_journal_issue                   18
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6282
_journal_page_last               6285
_journal_paper_doi               10.1021/jacs.7b00551
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H25 B F2 N2 O2'
_chemical_formula_sum            'C28 H25 B F2 N2 O2'
_chemical_formula_weight         470.31
_chemical_name_common            BAD1-BE
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2016-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.100(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9120(5)
_cell_length_b                   21.0584(7)
_cell_length_c                   7.2943(3)
_cell_measurement_reflns_used    8253
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.263
_cell_measurement_theta_min      3.679
_cell_volume                     2247.73(14)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker, 2014)'
_computing_data_collection       'APEX2 Ver. v.7-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker, 2014)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'D8 QUEST ECO'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            16154
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.265
_diffrn_reflns_theta_min         3.678
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.805
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0890 before and 0.0657 after correction.
The Ratio of minimum to maximum transmission is 0.8328.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.390
_exptl_crystal_description       Block
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
The compound was modelled in two parts which included a 
disordered BODIPY and epoxide moieties in a 75 and 25 % occupancy. 
Restrains (SADI) and constraints (EADP) were applied to the 
structure. Hydrogen atom attached to the tetrahydroanthra-
bis(oxirene) were freely refined over a generalized position 
of both disordered moieties and the restraint (DFIX) was applied. 
The structure was refined as a 2-component inversion twin. 
;
_refine_ls_abs_structure_Flack   0.3(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         4076
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0613
_refine_ls_R_factor_gt           0.0580
_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^)+(0.0946P)^2^+2.2619P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1602
_refine_ls_wR_factor_ref         0.1639
_reflns_Friedel_coverage         0.994
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3816
_reflns_number_total             4076
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00551_si_003.cif
_cod_data_source_block           kjf108_b
_cod_database_code               4126186
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.856
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7(4) 0.3(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C24-H24 = C23-H23 = C22-H22 = C21-H21
 0.89 with sigma of 0.01
 C31-H31 = C30-H30 = C29-H29 = C28-H28
 0.89 with sigma of 0.01
 C6-C19 \\sim C19-C6A
 with sigma of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(O33) = Uanis(O33A) = Uanis(O34A) = Uanis(O34)
Uanis(B12) = Uanis(B12A)
Uanis(F13) = Uanis(F14) = Uanis(F14A) = Uanis(F13A)
Uanis(N1) = Uanis(C5) = Uanis(C2) = Uanis(C4) = Uanis(C3) = Uanis(N1A) =
Uanis(C2A) = Uanis(C3A) = Uanis(C4A) = Uanis(C5A) = Uanis(N11) = Uanis(C8) =
Uanis(C7) = Uanis(C9) = Uanis(C10) = Uanis(C10A) = Uanis(C9A) = Uanis(C8A) =
Uanis(C7A) = Uanis(N11A)
Uanis(C6A) = Uanis(C6)
Uanis(C16) = Uanis(C16A) = Uanis(C15) = Uanis(C15A) = Uanis(C17) = Uanis(C17A)
= Uanis(C18A) = Uanis(C18)
5. Others
 Sof(N1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(C7A)=
 Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(N11A)=Sof(B12A)=Sof(F13A)=Sof(F14A)=
 Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(O33A)=Sof(O34A)=Sof(C18)=
 Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C18A)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(F14)=Sof(F13)=Sof(O34)=Sof(O33)=
 Sof(N1)=Sof(N11)=Sof(C17)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C9)=Sof(H9)=
 Sof(C2)=Sof(C3)=Sof(H3)=Sof(C8)=Sof(C4)=Sof(C10)=Sof(C5)=Sof(C16)=Sof(H16D)=
 Sof(H16E)=Sof(H16F)=Sof(C6)=Sof(C7)=Sof(C15)=Sof(H15D)=Sof(H15E)=Sof(H15F)=
 Sof(B12)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C9A(H9A), C9(H9), C3(H3)
6.b Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C15A(H15A,H15B,H15C), C16A(H16A,H16B,H16C), C17A(H17A,
 H17B,H17C), C18A(H18A,H18B,H18C), C17(H17D,H17E,H17F), C16(H16D,H16E,H16F),
 C18(H18D,H18E,H18F), C15(H15D,H15E,H15F)
;
_shelx_res_checksum              50453
_shelx_hkl_checksum              12810
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'