Confinement-Driven Photophysics in Cages, Covalent-Organic Frameworks, Metal-Organic Frameworks, and DNA.
Dolgopolova, Ekaterina A.; Berseneva, Anna A.; Faillace, Martín S; Ejegbavwo, Otega A.; Leith, Gabrielle A.; Choi, Seok W.; Gregory, Haley N.; Rice, Allison M.; Smith, Mark D.; Chruszcz, Maksymilian; Garashchuk, Sophya; Mythreye, Karthikeyan; Shustova, Natalia B.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b13505

data_4134306
_publ_section_title
;
 Confinement-Driven Photophysics in Cages, Covalent-Organic Frameworks,
 Metal-Organic Frameworks, and DNA.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b13505
_journal_year                    2020
_chemical_formula_moiety         '0.5(C191.2 H141.14 N9.03 O82.06 Zr12)'
_chemical_formula_sum            'C95.6 H70.57 N4.51 O41.03 Zr6'
_chemical_formula_weight         2486.34
_space_group_crystal_system      tetragonal
_space_group_IT_number           131
_space_group_name_Hall           '-P 4c 2'
_space_group_name_H-M_alt        'P 42/m m c'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   24.0073(12)
_cell_length_b                   24.0073(12)
_cell_length_c                   15.9595(8)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.416
_cell_measurement_theta_min      2.286
_cell_volume                     9198.3(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX3 v2016.5-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1319
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            117771
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.480
_diffrn_reflns_theta_max         26.482
_diffrn_reflns_theta_min         2.123
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.378
_exptl_absorpt_correction_T_max  0.8620
_exptl_absorpt_correction_T_min  0.8249
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0716 before and 0.0658 after correction.
The Ratio of minimum to maximum transmission is 0.9570.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.898
_exptl_crystal_description       prism
_exptl_crystal_F_000             2488
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.903
_refine_diff_density_min         -0.724
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     197
_refine_ls_number_reflns         5172
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0644
_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^)+(0.0896P)^2^+20.1929P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1685
_refine_ls_wR_factor_ref         0.1804
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3723
_reflns_number_total             5172
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13505_si_006.cif
_cod_data_source_block           ead224_v2_sq
_cod_original_cell_volume        9198.3(10)
_cod_original_formula_sum        'C95.60 H70.57 N4.51 O41.03 Zr6'
_cod_database_code               4134306
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.970
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C13
 1.48 with sigma of 0.015
 O11-C11
 1.2 with sigma of 0.015
 N11-C11 = N11-C13
 1.38 with sigma of 0.015
 N12-C12
 1.41 with sigma of 0.015
 N12-C13
 1.296 with sigma of 0.015
 C12-C11
 1.47 with sigma of 0.015
 C14-N11
 2.5 with sigma of 0.015
 C14-N12
 2.5 with sigma of 0.015
 N11-C15
 1.445 with sigma of 0.015
 C15-C11
 2.5 with sigma of 0.015
 C15-C13
 2.55 with sigma of 0.015
 C16A-C15 = C16B-C15
 1.5 with sigma of 0.015
 O6-C16A = O6-C16B
 1.25 with sigma of 0.015
 O7A-C16A = O7B-C16B
 1.25 with sigma of 0.015
 C17-C12
 1.34 with sigma of 0.015
 C18-C17
 1.45 with sigma of 0.015
 C23-C18 = C23-C22 = C22-C21 = C21-C20 = C20-C19 = C19-C18
 1.4 with sigma of 0.015
 C24-C21
 1.48 with sigma of 0.015
 N11-O11
 2.31 with sigma of 0.02
 O11-C12
 2.456 with sigma of 0.02
 C17-C11
 2.47 with sigma of 0.02
 C17-N12
 2.48 with sigma of 0.02
 C12-C18
 2.5 with sigma of 0.02
 C11-O11
 1.22 with sigma of 0.015
 H7-H14A_$1
 -2.1 with sigma of 0.02
 C17-C19 \\sim C17-C23
 with sigma of 0.015
 C18-C20 \\sim C19-C21 \\sim C20-C22 \\sim C21-C23 \\sim C22-C18 \\sim C19-C23
 with sigma of 0.01
3. Restrained planarity
 O11, C11, N11, C13, N12, C12, C14, C15, C17
 with sigma of 0.015
 C15, C16A, O7A, O6
 with sigma of 0.01
 C15, C16B, O6, O7B
 with sigma of 0.01
 C17, C18, C19, C20, C21, C24, O8, O9, C22, C23
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uiso(O7A) = Uiso(O7B) = Uiso(O8) = Uiso(O9) = Uiso(O11) = Uiso(N11) = Uiso(N12)
= Uiso(C11) = Uiso(C12) = Uiso(C13) = Uiso(C14) = Uiso(C15) = Uiso(C16A) =
Uiso(C16B) = Uiso(C17) = Uiso(C18) = Uiso(C19) = Uiso(C20) = Uiso(C21) =
Uiso(C22) = Uiso(C23) = Uiso(C24)
5. Others
 Sof(O8)=Sof(O9)=Sof(O11)=Sof(N11)=Sof(N12)=Sof(C11)=Sof(C12)=Sof(C13)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(C17)=Sof(H17)=Sof(C18)=
 Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(C22)=Sof(H22)=Sof(C23)=
 Sof(H23)=Sof(C24)=FVAR(1)
 Fixed Sof: O7A(0.111) O7B(0.171) H15A(0.111) H15B(0.111) H15C(0.171)
 H15D(0.171) C16A(0.111) C16B(0.171)
 Fixed Y: O6(0)
6.a Riding coordinates:
 C15(H15A,H15B,H15C,H15D)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C7(H7), C17(H17), C19(H19), C20(H20), C22(H22), C23(H23)
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              27685
_shelx_hkl_checksum              4123
_shelx_fab_checksum              8454
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'