Encapsulating electron-deficient dyes into Metal-Organic Capsules To Achieve High Reduction Potentials
Yuan, Jiayou; Wei, Zhong; Shen, Keshen; Yang, Yang; Liu, Mingxu; Jing, Xu; Duan, Chunying; Dalton Transactions  (2022) –; doi:10.1039/D2DT01166B

data_7710591
_publ_section_title
;
 Encapsulating electron-deficient dyes into Metal-Organic Capsules To
 Achieve High Reduction Potentials
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01166B
_journal_year                    2022
_chemical_formula_moiety
'C326 H239 N58 Zn8, 14.768(Cl O4), Cl O4.232, 8(C2 H3 N), 0.232(Cl O3)'
_chemical_formula_sum            'C342 H263 Cl16 N66 O64 Zn8'
_chemical_formula_weight         7411.33
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-04-13
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.03.08 svn.r54f81f84 for OlexSys, GUI svn.r6487)
;
_audit_update_record
;
2022-04-13 deposited with the CCDC.	2022-06-21 downloaded from the CCDC.
;
_cell_angle_alpha                97.486(7)
_cell_angle_beta                 95.237(7)
_cell_angle_gamma                105.524(7)
_cell_formula_units_Z            2
_cell_length_a                   23.386(7)
_cell_length_b                   24.387(8)
_cell_length_c                   38.081(11)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      26.857
_cell_measurement_theta_min      2.211
_cell_volume                     20566(11)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.00
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-III CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1426
_diffrn_reflns_av_unetI/netI     0.0909
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            770922
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.196
_exptl_absorpt_coefficient_mu    0.634
_exptl_absorpt_correction_T_max  0.0055
_exptl_absorpt_correction_T_min  0.0002
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1382 before and 0.0944 after correction.
The Ratio of minimum to maximum transmission is 0.0364.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic light red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.197
_exptl_crystal_description       block
_exptl_crystal_F_000             7602
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.29
_refine_diff_density_max         1.088
_refine_diff_density_min         -0.902
_refine_diff_density_rms         0.151
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     4672
_refine_ls_number_reflns         71175
_refine_ls_number_restraints     2344
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.1866
_refine_ls_R_factor_gt           0.1324
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w={1-exp[-5.0000(sin\q/\l)^2^)]}/[\s^2^(Fo^2^)+(0.0000P)^2^+10.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2191
_refine_ls_wR_factor_ref         0.2349
_reflns_Friedel_coverage         0.000
_reflns_number_gt                35638
_reflns_number_total             71175
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01166b2.cif
_cod_data_source_block           434324_0m
_cod_original_cell_volume        20565(11)
_cod_database_code               7710591
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.837
_shelx_estimated_absorpt_t_min   0.804
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N8-C335
 1.39 with sigma of 0.02
 C21B-C335 = C167-C335
 1.36 with sigma of 0.02
 Cl4A-O16
 1.44 with sigma of 0.02
3. Rigid bond restraints
 C346
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl2B, O8B, O13B, O29B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C21B, C73
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C21B, C335
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 C83, N01Q
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.1
 C335, C21B
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.1
 C83, C73
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.1
 C335, N8
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.1
 C335, C167
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.1
 C83, C333
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.1
4. Uiso/Uaniso restraints and constraints
C1 \\sim C4 \\sim C6 \\sim C8 \\sim C10 \\sim C12 \\sim C14 \\sim C16 \\sim C18
\\sim C20 \\sim C22 \\sim C24 \\sim C26 \\sim C28 \\sim C30 \\sim C32 \\sim C34
\\sim C36 \\sim C38 \\sim C40 \\sim C42 \\sim C44 \\sim C46 \\sim C48 \\sim C50
\\sim C52 \\sim C54 \\sim C56 \\sim C58 \\sim C60 \\sim C62 \\sim C64 \\sim C66
\\sim C68 \\sim C70 \\sim C72 \\sim C74 \\sim C76 \\sim C78 \\sim C80 \\sim C82
\\sim C84 \\sim C86 \\sim C88 \\sim C90 \\sim C92 \\sim C94 \\sim C96 \\sim C98
\\sim C100 \\sim C102 \\sim C104 \\sim C106 \\sim C108 \\sim C110 \\sim C112
\\sim C114 \\sim C116 \\sim C118 \\sim C120 \\sim C122 \\sim C124 \\sim C126
\\sim C128 \\sim C130 \\sim C132 \\sim C134 \\sim C136 \\sim C138 \\sim C140
\\sim C142 \\sim C144 \\sim C146 \\sim C148 \\sim C150 \\sim C152 \\sim C154
\\sim C156 \\sim C158 \\sim C160 \\sim C162 \\sim C164 \\sim C166 \\sim C168
\\sim C170 \\sim C172 \\sim C174 \\sim C176 \\sim C178 \\sim C180 \\sim C182
\\sim C184 \\sim C186 \\sim C188 \\sim C190 \\sim C192 \\sim C194 \\sim C196
\\sim C198 \\sim C200 \\sim C202 \\sim C204 \\sim C206 \\sim C208 \\sim C210
\\sim C212 \\sim C214 \\sim C216 \\sim C218 \\sim C220 \\sim C222 \\sim C224
\\sim C226 \\sim C228 \\sim C230 \\sim C232 \\sim C234 \\sim C236 \\sim C238
\\sim C240 \\sim C242 \\sim C244 \\sim C246 \\sim C248 \\sim C250 \\sim C252
\\sim C254 \\sim C256 \\sim C258 \\sim C260 \\sim C262 \\sim C264 \\sim C266
\\sim C268 \\sim C270 \\sim C272 \\sim C274 \\sim C276 \\sim C278 \\sim C280
\\sim C282 \\sim C284 \\sim C286 \\sim C288 \\sim C290 \\sim C292 \\sim C294
\\sim C296 \\sim C298 \\sim C300 \\sim C302 \\sim C304 \\sim C306 \\sim C308
\\sim C310 \\sim C312 \\sim C314 \\sim C316 \\sim C318 \\sim C320 \\sim C322
\\sim C324 \\sim C326 \\sim C328 \\sim C330 \\sim C332 \\sim C334 \\sim C336
\\sim C338 \\sim C340 \\sim C342 \\sim C344 \\sim C346 \\sim C348 \\sim C350
\\sim C175 \\sim C11 \\sim C177 \\sim C89 \\sim C179 \\sim C45 \\sim C181 \\sim
C91 \\sim C183 \\sim C23 \\sim C185 \\sim C93 \\sim C187 \\sim C47 \\sim C189
\\sim C95 \\sim C191 \\sim C3 \\sim C193 \\sim C97 \\sim C195 \\sim C49 \\sim
C197 \\sim C99 \\sim C199 \\sim C25 \\sim C201 \\sim C101 \\sim C203 \\sim C51
\\sim C205 \\sim C103 \\sim C207 \\sim C13 \\sim C209 \\sim C105 \\sim C211
\\sim C53 \\sim C213 \\sim C107 \\sim C215 \\sim C27 \\sim C217 \\sim C109
\\sim C219 \\sim C55 \\sim C221 \\sim C111 \\sim C223 \\sim C7 \\sim C225 \\sim
C113 \\sim C227 \\sim C57 \\sim C229 \\sim C115 \\sim C231 \\sim C29 \\sim C233
\\sim C117 \\sim C235 \\sim C59 \\sim C237 \\sim C119 \\sim C239 \\sim C15
\\sim C241 \\sim C121 \\sim C243 \\sim C61 \\sim C245 \\sim C123 \\sim C247
\\sim C31 \\sim C249 \\sim C125 \\sim C251 \\sim C63 \\sim C253 \\sim C127
\\sim C255 \\sim C2 \\sim C257 \\sim C129 \\sim C259 \\sim C65 \\sim C261 \\sim
C131 \\sim C263 \\sim C33 \\sim C265 \\sim C133 \\sim C267 \\sim C67B \\sim
C269 \\sim C135 \\sim C271 \\sim C17B \\sim C273 \\sim C137 \\sim C275 \\sim
C69 \\sim C277 \\sim C139 \\sim C279 \\sim C35 \\sim C281 \\sim C141 \\sim C283
\\sim C71 \\sim C285 \\sim C143 \\sim C287 \\sim C9 \\sim C289 \\sim C145 \\sim
C291 \\sim C73B \\sim C293 \\sim C147 \\sim C295 \\sim C37 \\sim C297 \\sim
C149 \\sim C299 \\sim C75 \\sim C301 \\sim C151 \\sim C303 \\sim C19 \\sim C305
\\sim C153 \\sim C17 \\sim C77B \\sim C309 \\sim C155 \\sim C311 \\sim C39
\\sim C313 \\sim C157 \\sim C67 \\sim C79 \\sim C317 \\sim C159 \\sim C319
\\sim C321 \\sim C161 \\sim C81 \\sim C325 \\sim C163 \\sim C327 \\sim C41
\\sim C329 \\sim C165 \\sim C73 \\sim C83 \\sim C333 \\sim C167 \\sim C335
\\sim C21B \\sim C337 \\sim C169 \\sim C339 \\sim C85 \\sim C341 \\sim C171
\\sim C343 \\sim C43 \\sim C345 \\sim C173 \\sim C347 \\sim C87 \\sim C349
\\sim C17A \\sim C67A \\sim C1A \\sim C77A \\sim C5 \\sim C73A \\sim C1B \\sim
C21A: within 2A with sigma of 3.8 and sigma for terminal atoms of 7.6 within 2A
Uanis(O8B) \\sim Ueq, Uanis(Cl2B) \\sim Ueq, Uanis(O13B) \\sim Ueq, Uanis(O29B)
\\sim Ueq, Uanis(O13A) \\sim Ueq, Uanis(O8A) \\sim Ueq, Uanis(Cl2A) \\sim Ueq,
Uanis(O29A) \\sim Ueq, Uanis(O9A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C349) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C21B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C313) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C335) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C83) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C73B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C73A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C77B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C73) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C67) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17B) \\sim Ueq, Uanis(C101) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O16) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Others
 Sof(Cl2B)=Sof(O8B)=Sof(O13B)=Sof(O29B)=1-FVAR(1)
 Sof(O8A)=Sof(Cl2A)=Sof(O13A)=Sof(O29A)=Sof(O9A)=FVAR(1)
 Sof(O0)=Sof(O30B)=1-FVAR(2)
 Sof(O8)=Sof(O30A)=FVAR(2)
 Sof(O5B)=1-FVAR(3)
 Sof(O5)=Sof(O5A)=FVAR(3)
 Sof(N0)=Sof(C67B)=Sof(H67B)=Sof(C17B)=Sof(H17B)=Sof(C17)=Sof(H17)=Sof(C77B)=
 Sof(H77B)=1-FVAR(4)
 Sof(N7)=Sof(C17A)=Sof(H17A)=Sof(C67A)=Sof(H67A)=Sof(C1A)=Sof(H1A)=Sof(C77A)=
 Sof(H77A)=FVAR(4)
 Sof(H97A)=Sof(H33A)=Sof(H14A)=Sof(H14B)=Sof(C73B)=Sof(C67)=Sof(H67)=1-FVAR(5)
 Sof(H97)=Sof(H33)=Sof(H141)=Sof(H143)=Sof(C5)=Sof(H5)=Sof(C73A)=FVAR(5)
 Sof(N8)=1-FVAR(6)
 Sof(N9)=FVAR(6)
 Sof(O15)=Sof(O10)=Sof(O12)=Sof(O13)=1-FVAR(7)
 Sof(O16)=Sof(O17)=Sof(O18)=Sof(O19)=FVAR(7)
 Fixed Sof: O9(0.55) C73(0.25) H73(0.25) C21B(0.25) H21B(0.25) C339(0.5)
 H339(0.5) C85(0.5) H85(0.5) C171(0.5) H171(0.5) C343(0.5) H343(0.5) C43(0.5)
 H43(0.5) C345(0.5) H345(0.5) C173(0.5) H173(0.5) C347(0.5) H347(0.5) C87(0.5)
 H87(0.5) C349(0.5) H349(0.5) C1B(0.25) H1B(0.25) C21A(0.25) H21A(0.25)
 Fixed X: Zn2(0.706829) Zn3(0.157741) Zn8(0.272169) Zn1(0.85498) Zn7(0.80765)
 Zn4(0.334579) Zn6(0.88509) Zn5(0.347381) C14(0.433439) O9(0.09501)
 C109(0.792429) O8B(0.470949) O13B(0.368061) O29B(0.359529) O29A(0.388381)
 C1B(0.22075) Cl4A(0.92682)
 Fixed Y: Zn2(0.904809) Zn3(0.76183) Zn8(0.353181) Zn1(1.200629) Zn7(0.462029)
 Zn4(1.04696) Zn6(0.750469) Zn5(0.59754) C14(0.55974) O9(0.46492) C109(0.65935)
 O8B(0.71357) O13B(0.678221) O29B(0.73806) O29A(0.714409) C1B(0.923861)
 Cl4A(0.54974)
 Fixed Z: Zn2(0.51921) Zn3(0.54497) Zn8(0.67225) Zn1(0.818271) Zn7(0.63308)
 Zn4(0.86273) Zn6(0.935669) Zn5(0.99356) C14(0.936659) O9(0.60218)
 C109(0.79151) O8B(0.6302) O13B(0.634409) O29B(0.627251) O29A(0.61713)
 C1B(0.772519) Cl4A(0.79583)
6.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C12(H12), C16(H16), C18(H18), C22(H22), C24(H24), N02S(H02S),
 C30(H30), C32(H32), C34(H34), C38(H38), C46(H46), C56(H56), C58(H58), C64(H64),
  C66(H66), C70(H70), C72(H72), C76(H76), C88(H88), C92(H92), C94(H94),
 C96(H96), C112(H112), C114(H114), C116(H116), C120(H120), C122(H122),
 C124(H124), C128(H128), C130(H130), C138(H138), C142(H142), C144(H144),
 C148(H148), C156(H156), C160(H160), C162(H162), C168(H168), C170(H170),
 C172(H172), C174(H174), C176(H176), C178(H178), C182(H182), C186(H186),
 C188(H188), C192(H192), C194(H194), C196(H196), C198(H198), C200(H200),
 C204(H204), C208(H208), C210(H210), C214(H214), C216(H216), C218(H218),
 C220(H220), C224(H224), C226(H226), C228(H228), C230(H230), C236(H236),
 C238(H238), C240(H240), C242(H242), C244(H244), C248(H248), C250(H250),
 C252(H252), C256(H256), C258(H258), C260(H260), C264(H264), C266(H266),
 C272(H272), C274(H274), C276(H276), C278(H278), C280(H280), C282(H282),
 C284(H284), C286(H286), C288(H288), C292(H292), C294(H294), C296(H296),
 C298(H298), C300(H300), C302(H302), C304(H304), C310(H310), C312(H312),
 C314(H314), C320(H320), C322(H322), C324(H324), C328(H328), C330(H330),
 C334(H334), C338(H338), C342(H342), C344(H344), C346(H346), C350(H350),
 C175(H175), C11(H11), C89(H89), C179(H179), C45(H45), C181(H181), C91(H91),
 C183(H183), C23(H23), C185(H185), C93(H93), C187(H187), C47(H47), C189(H189),
 C191(H191), C3(H3), C193(H193), C97(H97A), C97(H97), C195(H195), C49(H49),
 C197(H197), C199(H199), C25(H25), C201(H201), C101(H101), C203(H203), C51(H51),
  C205(H205), C13(H13), C105(H105), C211(H211), C53(H53), C213(H213),
 C107(H107), C215(H215), C27(H27), C109(H109), C219(H219), C55(H55), C221(H221),
  C223(H223), C7(H7), C225(H225), C113(H113), C227(H227), C57(H57), C229(H229),
 C115(H115), C231(H231), C29(H29), C117(H117), C235(H235), C59(H59), C237(H237),
  C119(H119), C239(H239), C15(H15), C241(H241), C243(H243), C245(H245),
 C123(H123), C31(H31), C249(H249), C125(H125), C251(H251), C63(H63), C253(H253),
  C127(H127), C255(H255), C2(H2), C257(H257), C129(H129), C65(H65), C131(H131),
 C263(H263), C33(H33A), C33(H33), C265(H265), C133(H133), C267(H267),
 C67B(H67B), C269(H269), C271(H271), C17B(H17B), C273(H273), C137(H137),
 C275(H275), C69(H69), C277(H277), C139(H139), C279(H279), C281(H281),
 C141(H14A), C141(H141), C283(H283), C71(H71), C285(H285), C143(H14B),
 C143(H143), C287(H287), C289(H289), C145(H145), C291(H291), C293(H293),
 C147(H147), C295(H295), C37(H37), C297(H297), C149(H149), C299(H299), C75(H75),
  C301(H301), C303(H303), C153(H153), C17(H17), C77B(H77B), C155(H155),
 C311(H311), C39(H39), C313(H313), C157(H157), C67(H67), C159(H159), C321(H321),
  C161(H161), C163(H163), C327(H327), C73(H73), C333(H333), C167(H167),
 C21B(H21B), C337(H337), C339(H339), C85(H85), C171(H171), C343(H343), C43(H43),
  C345(H345), C173(H173), C347(H347), C87(H87), C349(H349), C17A(H17A),
 C67A(H67A), C1A(H1A), C77A(H77A), C5(H5), C1B(H1B)
6.b Fitted hexagon refined as free rotating group:
 C73(C83,C333,C167,C335,C21B)
6.c Idealised Me refined as rotating group:
 C111(H11A,H11B,H11C), C151(H15A,H15B,H15C), C309(H30A,H30B,H30C), C79(H79A,
 H79B,H79C), C317(H31A,H31B,H31C), C81(H81A,H81B,H81C), C329(H32A,H32B,H32C),
 C165(H16A,H16B,H16C)
;
_shelx_res_checksum              89133
_olex2_submission_special_instructions 'No special instructions were received'