All Roads Lead to Rome: Tuning the Luminescence of a Breathing Catenated Zr-MOF by Programmable Multiplexing Pathways
Chen, Cheng-Xia; Wei, Zhang-Wen; Cao, Chen-Chen; Yin, Shao-Yun; Qiu, Qian-Feng; Zhu, Neng-Xiu; Xiong, Yang-Yang; Jiang, Ji-Jun; Pan, Mei; Su, Cheng-Yong; Chemistry of Materials 31 (2019) 5550–; doi:10.1021/acs.chemmater.9b01258

data_4003040
_publ_section_title
;
 All Roads Lead to Rome: Tuning the Luminescence of a Breathing Catenated
 Zr-MOF by Programmable Multiplexing Pathways
;
_journal_issue                   15
_journal_name_full               'Chemistry of Materials'
_journal_page_first              5550
_journal_paper_doi               10.1021/acs.chemmater.9b01258
_journal_volume                  31
_journal_year                    2019
_chemical_formula_moiety
'0.25(C216 H128 O64 Zr12), 0.25(C108 H64 O36 Zr8), 0.25(C108 H64 O28 Zr4)'
_chemical_formula_sum            'C108 H64 O32 Zr6'
_chemical_formula_weight         2420.91
_chemical_name_common            LIFM-114-80C
_space_group_crystal_system      orthorhombic
_space_group_IT_number           65
_space_group_name_Hall           '-C 2 2'
_space_group_name_H-M_alt        'C m m m'
_symmetry_space_group_name_Hall  '-C 2 2'
_symmetry_space_group_name_H-M   'C m m m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.0637(7)
_cell_length_b                   42.3687(11)
_cell_length_c                   18.0144(4)
_cell_measurement_reflns_used    6358
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      65.4670
_cell_measurement_theta_min      4.7090
_cell_volume                     16076.8(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -65.00  22.00   1.00   18.00    --    1.62 -37.00 150.00   87
  2  \w     59.00  85.00   1.00   22.00    --   88.73  77.00 -90.00   26
  3  \w    122.00 155.00   1.00   22.00    --   88.73  77.00 -90.00   33
  4  \w    110.00 157.00   1.00   22.00    --   88.73 125.00 120.00   47
  5  \w     15.00 100.00   1.00   22.00    --   88.73 -30.00 120.00   85
  6  \w    117.00 159.00   1.00   22.00    --   88.73 125.00-150.00   42
  7  \w     26.00  59.00   1.00   22.00    --   88.73 -15.00 -30.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0220780000
_diffrn_orient_matrix_UB_12      0.0243904000
_diffrn_orient_matrix_UB_13      0.0580484000
_diffrn_orient_matrix_UB_21      0.0601974000
_diffrn_orient_matrix_UB_22      0.0064658000
_diffrn_orient_matrix_UB_23      -0.0461011000
_diffrn_orient_matrix_UB_31      -0.0351125000
_diffrn_orient_matrix_UB_32      0.0262132000
_diffrn_orient_matrix_UB_33      -0.0425735000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            17653
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        65.687
_diffrn_reflns_theta_max         65.687
_diffrn_reflns_theta_min         3.768
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.515
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.000
_exptl_crystal_description       prism
_exptl_crystal_F_000             4832
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_platon_squeeze_details
;
TITL 18062704 in Cmmm
CELL   21.0637   42.3687   18.0144     90.00     90.00     90.00
SPGR Cmmm
C101 1.000 0.448 0.248 !       2.84 eA-3
C102 0.658 0.133-0.002 !       2.37 eA-3
Q103 0.500 0.468 0.367 !       2.17 eA-3
C104 0.221 0.094 0.003 !       2.05 eA-3
C105 0.733 0.102 0.490 !       1.98 eA-3
C106 0.278 0.045 0.405 !       1.97 eA-3
C107 0.500 0.156 0.000 !       1.79 eA-3
C108 0.500 0.070 0.380 !       1.79 eA-3
Q109 0.791 0.445 0.043 !       1.70 eA-3
C110 0.236 0.046 0.143 !       1.60 eA-3
Q111 1.000 0.055 0.267 !       1.58 eA-3
Q112 0.719 0.445 0.407 !       1.57 eA-3
C113 1.000 0.195 0.496 !       1.57 eA-3
C114 0.380 0.117 0.504 !       1.56 eA-3
C115 0.500 0.062 0.317 !       1.50 eA-3
C116 0.270 0.453 0.095 !       1.49 eA-3
Q117 0.500 0.039 0.116 !       1.48 eA-3
C118 0.500 0.185 0.037 !       1.47 eA-3
C119 0.500 0.439 0.190 !       1.45 eA-3
C120 0.841 0.393 0.488 !       1.44 eA-3
C121 0.500 0.113 0.358 !       1.44 eA-3
C122 0.493 0.090 0.373 !       1.42 eA-3
C123 0.453 0.185 0.050 !       1.39 eA-3
C124 0.894 0.483 0.390 !       1.39 eA-3
C125 0.294 0.024 0.279 !       1.39 eA-3
C126 0.118 0.498 0.484 !       1.37 eA-3
Q127 0.597 0.041 0.324 !       1.35 eA-3
C128 0.591 0.188-0.005 !       1.34 eA-3
C129 0.500 0.139 0.426 !       1.27 eA-3
C130 0.500 0.195 0.095 !       1.27 eA-3
Q131 0.231 0.470 0.065 !       1.25 eA-3
C132 0.266 0.394 0.470 !       1.24 eA-3
C133 1.000 0.212 0.202 !       1.22 eA-3
C134 1.000 0.453 0.439 !       1.22 eA-3
C135 1.000 0.336 0.475 !       1.21 eA-3
C136 0.143 0.117 0.001 !       1.21 eA-3
C137 0.264 0.062 0.504 !       1.19 eA-3
C138 1.000 0.277 0.144 !       1.18 eA-3
Q139 0.987 0.484 0.093 !       1.16 eA-3
C140 0.680 0.078-0.003 !       1.16 eA-3
C141 0.782 0.429 0.439 !       1.16 eA-3
C142 0.608 0.030 0.434 !       1.16 eA-3
Q143 0.625 0.009 0.330 !       1.15 eA-3
C144 0.200 0.500 0.500 !       1.15 eA-3
Q145 0.801 0.008 0.251 !       1.15 eA-3
C146 0.440 0.500 0.000 !       1.14 eA-3
Q147 0.600 0.031 0.004 !       1.13 eA-3
Q148 0.355 0.502 0.172 !       1.13 eA-3
Q149 1.000 0.501 0.031 !       1.12 eA-3
C150 1.000 0.241 0.266 !       1.12 eA-3
C151 0.500 0.285 0.287 !       1.10 eA-3
Q152 0.107 0.016 0.501 !       1.08 eA-3
C153 0.264 0.063 0.009 !       1.07 eA-3
C154 1.000 0.223 0.307 !       1.07 eA-3
Q155 1.000 0.470 0.068 !       1.06 eA-3
C156 0.467 0.177 0.070 !       1.05 eA-3
Q157 0.723 0.014 0.097 !       1.05 eA-3
C158 0.590 0.156 0.496 !       1.04 eA-3
C159 0.918 0.203 0.494 !       1.04 eA-3
C160 0.970 0.317 0.471 !       1.04 eA-3
C161 0.448 0.251 0.220 !       1.02 eA-3
C162 0.967 0.210 0.335 !       1.02 eA-3
Q163 0.196 0.503 0.062 !       1.01 eA-3
C164 0.950 0.279 0.120 !       1.01 eA-3
C165 0.486 0.500 0.000 !       1.01 eA-3
C166 1.000 0.462 0.303 !       1.00 eA-3
C167 0.544 0.164 0.508 !       1.00 eA-3
C168 0.467 0.237 0.094 !       1.00 eA-3
Q169 0.795 0.484 0.440 !       0.99 eA-3
C170 0.500 0.300 0.143 !       0.99 eA-3
C171 1.000 0.140 0.032 !       0.99 eA-3
C172 0.812 0.502 0.344 !       0.99 eA-3
C173 0.987 0.258 0.173 !       0.98 eA-3
C174 0.167 0.476 0.355 !       0.98 eA-3
C175 0.765 0.070 0.005 !       0.98 eA-3
C176 0.315 0.094 0.001 !       0.97 eA-3
C177 0.500 0.310 0.179 !       0.97 eA-3
Q178 0.566 0.017 0.328 !       0.96 eA-3
Q179 0.280 0.475 0.281 !       0.96 eA-3
Q180 0.090 0.190 0.435 !       0.96 eA-3
Q181 0.982 0.475 0.263 !       0.95 eA-3
Q182 0.285 0.498 0.281 !       0.94 eA-3
Q183 0.579 0.500 0.156 !       0.94 eA-3
Q184 0.063 0.486 0.259 !       0.94 eA-3
Q185 0.706 0.469 0.468 !       0.93 eA-3
Q186 0.308 0.500 0.469 !       0.92 eA-3
C187 0.491 0.321 0.138 !       0.92 eA-3
Q188 0.824 0.086 0.503 !       0.92 eA-3
C189 0.914 0.281 0.110 !       0.91 eA-3
C190 0.530 0.224 0.472 !       0.89 eA-3
C191 0.081 0.437 0.390 !       0.89 eA-3
C192 1.000 0.269 0.442 !       0.88 eA-3
Q193 0.725 0.498 0.188 !       0.88 eA-3
Q194 0.683 0.039 0.003 !       0.87 eA-3
C195 0.500 0.031 0.507 !       0.87 eA-3
Q196 0.500 0.016-0.006 !       0.86 eA-3
C197 0.828 0.389 0.040 !       0.86 eA-3
Q198 0.136 0.031 0.496 !       0.86 eA-3
Q199 0.546 0.354 0.108 !       0.86 eA-3
;
_refine_diff_density_max         2.015
_refine_diff_density_min         -4.000
_refine_diff_density_rms         0.245
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         7306
_refine_ls_number_restraints     950
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.1524
_refine_ls_R_factor_gt           0.1360
_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^)+(0.2000P)^2^+600.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3562
_refine_ls_wR_factor_ref         0.3721
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5782
_reflns_number_total             7306
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            LIFM-114-80C.cif
_cod_data_source_block           114-80C
_cod_database_code               4003040
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O Zr'
_chemical_oxdiff_usercomment     114-80
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.334
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 6(10)
 -5(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 C8-C9 = C9-C10 = C10-C11 = C11-C12
 1.39 with sigma of 0.01
 C12-C13 = C13-C8
 1.39 with sigma of 0.01
 C8-C10 = C9-C11 = C10-C12
 2.4 with sigma of 0.01
 C11-C13 = C12-C8 = C13-C9
 2.4 with sigma of 0.01
 C8-C11 = C9-C12 = C10-C13
 2.8 with sigma of 0.01
 C8-C9A = C9A-C10A = C10A-C11
 1.39 with sigma of 0.01
 C11-C12A = C12A-C13A = C13A-C8
 1.39 with sigma of 0.01
 C8-C10A = C9A-C11 = C10A-C12A
 2.4 with sigma of 0.01
 C11-C13A = C12A-C8 = C13A-C9A
 2.4 with sigma of 0.01
 C9A-C12A = C10A-C13A
 2.8 with sigma of 0.01
 C15-C16 = C19-C22 = C28-C25
 1.5 with sigma of 0.01
 C30-C29 = C33-C36 = C39-C42
 1.5 with sigma of 0.01
 C16-C17 = C17-C18 = C18-C19
 1.39 with sigma of 0.01
 C19-C20 = C20-C21 = C21-C16
 1.39 with sigma of 0.01
 C16-C18 = C17-C19 = C18-C20
 2.4 with sigma of 0.01
 C19-C21 = C20-C16 = C21-C17
 2.4 with sigma of 0.01
 C16-C19 = C17-C20 = C18-C21
 2.8 with sigma of 0.01
 C22-C23 = C23-C24 = C24-C25
 1.39 with sigma of 0.01
 C25-C26 = C26-C27 = C27-C22
 1.39 with sigma of 0.01
 C22-C24 = C23-C25 = C24-C26
 2.4 with sigma of 0.01
 C25-C27 = C26-C22 = C27-C23
 2.4 with sigma of 0.01
 C22-C25 = C23-C26 = C24-C27
 2.8 with sigma of 0.01
 C30-C31 = C31-C32 = C32-C33
 1.39 with sigma of 0.01
 C33-C34 = C34-C35 = C35-C30
 1.39 with sigma of 0.01
 C30-C32 = C31-C33 = C32-C34
 2.4 with sigma of 0.01
 C33-C35 = C34-C30 = C35-C31
 2.4 with sigma of 0.01
 C30-C33 = C31-C34 = C32-C35
 2.8 with sigma of 0.01
 C36-C37 = C37-C38 = C38-C39
 1.39 with sigma of 0.01
 C39-C40 = C40-C41 = C41-C36
 1.39 with sigma of 0.01
 C36-C38 = C37-C39 = C38-C40
 2.4 with sigma of 0.01
 C39-C41 = C40-C36 = C41-C37
 2.4 with sigma of 0.01
 C36-C39 = C37-C40 = C38-C41
 2.8 with sigma of 0.01
 C28-C42
 1.26 with sigma of 0.02
 Zr5-O13
 2.2 with sigma of 0.02
 C28-C26 \\sim C28-C24
 with sigma of 0.02
 C42-C40 \\sim C42-C38
 with sigma of 0.02
 O11-O12 \\sim O13-O14
 with sigma of 0.02
 Zr4-O16 \\sim Zr3-O16
 with sigma of 0.03
4. Restrained planarity
 C8, C9, C10, C11, C12, C13
 with sigma of 0.01
 C8, C9A, C10A, C12A, C13A, C11
 with sigma of 0.01
 C16, C17, C18, C19, C20, C21
 with sigma of 0.01
 C22, C23, C24, C25, C26, C27, H26
 with sigma of 0.01
 C30, C31, C32, C33, C34, C35
 with sigma of 0.01
 C36, C37, C38, C39, C40, C41
 with sigma of 0.01
 Zr4, Zr5, O11, O12, O13, O14
 with sigma of 0.01
5. Rigid bond restraints
 C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29,
 C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, O3, O4, O5, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C9A, C10A, C12A,
 C13A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Zr4, Zr5, O11, O12, O13, O14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Zr1, Zr2, O9, O10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim
C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim
C39 \\sim C40 \\sim C41 \\sim C42 \\sim O3 \\sim O4 \\sim O5 \\sim O6: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C9A \\sim C10A \\sim
C12A \\sim C13A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Zr4 \\sim Zr5 \\sim O11 \\sim O12 \\sim O13 \\sim O14: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
Zr1 \\sim Zr2 \\sim O9 \\sim O10: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C10A)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(O17) \\sim Ueq, Uanis(O13) \\sim Ueq,
Uanis(O1) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O10) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O8) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
7. Others
 Fixed Sof: Zr3(0.25) Zr4(0.25) Zr5(0.25) O3(0.5) O4(0.5) O5(0.5) O6(0.5)
 O11(0.25) O12(0.25) O13(0.25) O14(0.25) O15(0.5) O16(0.25) O17(0.25) C9(0.5)
 H9(0.5) C10(0.5) H10(0.5) C12(0.5) H12(0.5) C13(0.5) H13(0.5) C15(0.5)
 C16(0.5) C17(0.5) H17(0.5) C18(0.5) H18(0.5) C19(0.5) C20(0.5) H20(0.5)
 C21(0.5) H21(0.5) C22(0.5) C23(0.5) H23(0.5) C24(0.5) H24(0.5) C25(0.5)
 C26(0.5) H26(0.5) C27(0.5) H27(0.5) C29(0.5) C30(0.5) C31(0.5) H31(0.5)
 C32(0.5) H32(0.5) C33(0.5) C34(0.5) H34(0.5) C35(0.5) H35(0.5) C36(0.5)
 C37(0.5) H37(0.5) C38(0.5) H38(0.5) C39(0.5) C40(0.5) H40(0.5) C41(0.5)
 H41(0.5) C42(0.25) C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5) C12A(0.5) H12A(0.5)
 C13A(0.5) H13A(0.5)
8.a Riding coordinates:
 C26(H26)
8.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24), C27(H27), C31(H31),
  C32(H32), C34(H34), C35(H35), C37(H37), C38(H38), C40(H40), C41(H41),
 C9A(H9A), C10A(H10A), C12A(H12A), C13A(H13A)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 5.355
_oxdiff_exptl_absorpt_empirical_full_min 0.521