Tailored homo- and hetero- lanthanide porphyrin dimers: a synthetic strategy for integrating multiple spintronic functionalities into a single molecule.
Le Roy, Jennifer J.; Cremers, Jonathan; Thomlinson, Isabel A.; Slota, Michael; Myers, William K.; Horton, Peter H.; Coles, Simon J.; Anderson, Harry L.; Bogani, Lapo; Chemical science 9 (2018) 8474–8481; doi:10.1039/c8sc03762k

data_1550076
_publ_section_title
;
 Tailored homo- and hetero- lanthanide porphyrin dimers: a synthetic
 strategy for integrating multiple spintronic functionalities into a
 single molecule.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              8474
_journal_page_last               8481
_journal_paper_doi               10.1039/c8sc03762k
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C87 H127 Co N4 O9 P3 Si2 Tb, 1.5(CH2Cl2)'
_chemical_formula_sum            'C88.5 H130 Cl3 Co N4 O9 P3 Si2 Tb'
_chemical_formula_weight         1867.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-26
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.07.04 svn.r3439 for OlexSys, GUI svn.r5361)
;
_audit_update_record
;
2017-07-27 deposited with the CCDC.
2018-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.3060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.5498(4)
_cell_length_b                   16.09500(10)
_cell_length_c                   19.4714(2)
_cell_measurement_reflns_used    96961
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.1670
_cell_measurement_theta_min      1.8290
_cell_volume                     9439.85(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28e (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_temperature      100(2)
_diffrn_detector                 'hybrid pixel detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -66.00  67.00   0.50   13.00    --  -22.80  57.00-150.00  266
  2  \w    -66.00  67.00   0.50   13.00    --  -22.80  57.00  90.00  266
  3  \w    -66.00  67.00   0.50   13.00    --  -22.80  65.00 -90.00  266
  4  \w    -66.00  67.00   0.50   13.00    --  -22.80  65.00 120.00  266
  5  \w    -66.00  67.00   0.50   13.00    --  -22.80  65.00   0.00  266
  6  \w    -66.00  67.00   0.50   13.00    --  -22.80  65.00-180.00  266
  7  \w    -66.00  67.00   0.50   13.00    --  -22.80  65.00 -30.00  266
  8  \w   -112.00  21.00   0.50   13.00    --  -22.80 -65.00  90.00  266
  9  \w   -112.00  21.00   0.50   13.00    --  -22.80 -57.00 150.00  266
 10  \w   -112.00  21.00   0.50   13.00    --  -22.80 -57.00 -30.00  266
 11  \w   -112.00  21.00   0.50   13.00    --  -22.80 -65.00-150.00  266
 12  \w   -112.00  21.00   0.50   13.00    --  -22.80 -65.00  30.00  266
 13  \w   -112.00  21.00   0.50   13.00    --  -22.80 -65.00 -90.00  266
 14  \w   -112.00  -2.00   0.50   13.00    --  -22.80 -65.00 -30.00  220
 15  \w   -112.00  21.00   0.50   13.00    --  -22.80 -65.00 150.00  266
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, AFC11 quarter \c goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with VHF Varimax confocal mirrors and an AFC12 goniometer and HyPix 6000 detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroLoop'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0027497000
_diffrn_orient_matrix_UB_12      0.0075029000
_diffrn_orient_matrix_UB_13      0.0343243000
_diffrn_orient_matrix_UB_21      0.0233787000
_diffrn_orient_matrix_UB_22      -0.0001332000
_diffrn_orient_matrix_UB_23      0.0156166000
_diffrn_orient_matrix_UB_31      0.0005547000
_diffrn_orient_matrix_UB_32      0.0434113000
_diffrn_orient_matrix_UB_33      -0.0058862000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, VHF Varimax'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0656
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            315944
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         1.852
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_power             2.475
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku FRE+'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    1.134
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.348
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28e (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'iridescent purple'
_exptl_crystal_colour_primary    'iridescent purple'
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       plate
_exptl_crystal_F_000             3908
_exptl_crystal_recrystallization_method
'The material was obtained from a mixture of methanol and DCM'
_exptl_crystal_size_max          0.319
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.041
_refine_diff_density_max         1.928
_refine_diff_density_min         -1.148
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1228
_refine_ls_number_reflns         21622
_refine_ls_number_restraints     3508
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1022
_refine_ls_R_factor_gt           0.0872
_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^)+(0.1460P)^2^+35.4756P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2518
_refine_ls_wR_factor_ref         0.2681
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17246
_reflns_number_total             21622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03762k2.cif
_cod_data_source_block           P1Tb
_cod_depositor_comments
'Adding full bibliography for 1550065--1550077.cif.'
_cod_original_formula_sum        'C88.50 H130 Cl3 Co N4 O9 P3 Si2 Tb'
_cod_database_code               1550076
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C55H83 (C14H21)2 Co N4 O9 P3 Si2 Tb'
_chemical_oxdiff_usercomment     Tb-Por
_shelx_estimated_absorpt_t_max   0.955
_shelx_estimated_absorpt_t_min   0.714
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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. Restrained distances
 O206-C205 = O207-C207 = O208-C209 = O209-C211 = O204-C201 = O205-C203
 1.45 with sigma of 0.04
 Si1-C23 \\sim Si1-C26 \\sim Si1-C29 \\sim Si2-C40 \\sim Si2-C34 \\sim Si2-C37
 with sigma of 0.02
 C25-C24 \\sim C27-C28 \\sim C30-C31 \\sim C35-C36 \\sim C38-C39 \\sim C41-C42
 with sigma of 0.02
 C31-C29 \\sim C29-C30 \\sim C28-C26 \\sim C26-C27 \\sim C25-C23 \\sim C23-C24
 with sigma of 0.02
 C35-C34 \\sim C34-C36 \\sim C41-C40 \\sim C40-C42 \\sim C39-C37 \\sim C37-C38
 with sigma of 0.02
 C39-Si2 \\sim Si2-C38 \\sim C42-Si2 \\sim Si2-C41 \\sim C36-Si2 \\sim Si2-C35
 with sigma of 0.02
 C30-Si1 \\sim Si1-C31 \\sim C24-Si1 \\sim Si1-C25 \\sim C28-Si1 \\sim Si1-C27
 with sigma of 0.02
 C68-C61 \\sim C61-C69 \\sim C61-C70 \\sim C65-C59 \\sim C59-C66 \\sim C59-C64
 with sigma of 0.02
 C50-C45 \\sim C45-C51 \\sim C45-C52 \\sim C56-C47 \\sim C47-C55 \\sim C47-C54
 with sigma of 0.02
 C63-C59 \\sim C67-C61 \\sim C49-C45 \\sim C53-C47
 with sigma of 0.02
 C59-C64 \\sim C59-C65 \\sim C59-C66 \\sim C64-C65 \\sim C65-C66
 with sigma of 0.04
 C63-C59 \\sim C63-C64 \\sim C63-C65 \\sim C63-C66
 with sigma of 0.02
 C61-C68 \\sim C61-C69 \\sim C68-C70 \\sim C69-C70
 with sigma of 0.04
 C67-C61 \\sim C67-C68 \\sim C67-C69 \\sim C67-C70
 with sigma of 0.02
 C45-C50 \\sim C45-C51 \\sim C45-C52 \\sim C50-C51 \\sim C50-C52 \\sim C51-C52
 with sigma of 0.04
 C49-C45 \\sim C49-C50 \\sim C49-C51 \\sim C49-C52
 with sigma of 0.02
 C47-C54 \\sim C47-C55 \\sim C47-C56 \\sim C54-C55 \\sim C54-C56 \\sim C55-C56
 with sigma of 0.04
 C53-C47 \\sim C53-C54 \\sim C53-C55 \\sim C53-C56
 with sigma of 0.02
 O106-C105 \\sim O107-C107 \\sim O108-C109 \\sim O109-C111 \\sim O104-C101
\\sim O105-C103
 with sigma of 0.02
 C106-C105 \\sim C108-C107 \\sim C110-C109 \\sim C112-C111 \\sim C102-C101
\\sim C104-C103
 with sigma of 0.02
 P102-O107 \\sim P102-O106 \\sim P103-O108 \\sim P103-O109 \\sim P101-O104
\\sim P101-O105
 with sigma of 0.02
 C106-O106 \\sim C108-O107 \\sim C110-O108 \\sim O109-C112 \\sim O104-C102
\\sim O105-C104
 with sigma of 0.02
 P102-O102 \\sim P103-O103 \\sim P101-O101
 with sigma of 0.02
 O104-O105 \\sim O106-O107 \\sim O108-O109
 with sigma of 0.02
 O206-C205 \\sim O207-C207 \\sim O208-C209 \\sim O209-C211 \\sim O204-C201
\\sim O205-C203
 with sigma of 0.02
 C206-C205 \\sim C208-C207 \\sim C210-C209 \\sim C212-C211 \\sim C202-C201
\\sim C204-C203
 with sigma of 0.02
 P202-O207 \\sim P202-O206 \\sim P203-O208 \\sim P203-O209 \\sim P201-O204
\\sim P201-O205
 with sigma of 0.02
 C206-O206 \\sim C208-O207 \\sim C210-O208 \\sim O209-C212 \\sim O204-C202
\\sim O205-C204
 with sigma of 0.02
 P202-O202 \\sim P203-O203 \\sim P201-O201
 with sigma of 0.02
 O204-O205 \\sim O206-O207 \\sim O208-O209
 with sigma of 0.02
 Co2-C222 \\sim Co2-C221 \\sim Co2-C223 \\sim Co2-C225 \\sim Co2-C224
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{P101, P102, P103, O101, O102, O103, O104, O105, O106, O107, O108, O109, C101,
C102, C103, C104, C105, C106, C107, C108, C109, C110, C111, C112} sigma for
1-2: 0.02, 1-3: 0.04
as
{P201, P202, P203, O201, O202, O203, O204, O205, O206, O207, O208, O209, C201,
C202, C203, C204, C205, C206, C207, C208, C209, C210, C211, C212}
6. Others
 Sof(Tb2)=1-FVAR(1)
 Sof(Tb1)=FVAR(1)
 Sof(Co2)=Sof(C221)=Sof(H221)=Sof(C222)=Sof(H222)=Sof(C223)=Sof(H223)=
 Sof(C224)=Sof(H224)=Sof(C225)=Sof(H225)=1-FVAR(2)
 Sof(Co1)=Sof(C121)=Sof(H121)=Sof(C122)=Sof(H122)=Sof(C123)=Sof(H123)=
 Sof(C124)=Sof(H124)=Sof(C125)=Sof(H125)=FVAR(2)
 Sof(P201)=Sof(P202)=Sof(P203)=Sof(O201)=Sof(O202)=Sof(O203)=Sof(O204)=
 Sof(O205)=Sof(O206)=Sof(O207)=Sof(O208)=Sof(O209)=Sof(C201)=Sof(H20A)=
 Sof(H20B)=Sof(C202)=Sof(H20C)=Sof(H20D)=Sof(H20E)=Sof(C203)=Sof(H20F)=
 Sof(H20G)=Sof(C204)=Sof(H20H)=Sof(H20I)=Sof(H20J)=Sof(C205)=Sof(H20K)=
 Sof(H20L)=Sof(C206)=Sof(H20M)=Sof(H20N)=Sof(H20O)=Sof(C207)=Sof(H20P)=
 Sof(H20Q)=Sof(C208)=Sof(H20R)=Sof(H20S)=Sof(H20T)=Sof(C209)=Sof(H20U)=
 Sof(H20V)=Sof(C210)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C211)=Sof(H21D)=
 Sof(H21E)=Sof(C212)=Sof(H21F)=Sof(H21G)=Sof(H21H)=1-FVAR(3)
 Sof(P101)=Sof(P102)=Sof(P103)=Sof(O101)=Sof(O102)=Sof(O103)=Sof(O104)=
 Sof(O105)=Sof(O106)=Sof(O107)=Sof(O108)=Sof(O109)=Sof(C101)=Sof(H10A)=
 Sof(H10B)=Sof(C102)=Sof(H10C)=Sof(H10D)=Sof(H10E)=Sof(C103)=Sof(H10F)=
 Sof(H10G)=Sof(C104)=Sof(H10H)=Sof(H10I)=Sof(H10J)=Sof(C105)=Sof(H10K)=
 Sof(H10L)=Sof(C106)=Sof(H10M)=Sof(H10N)=Sof(H10O)=Sof(C107)=Sof(H10P)=
 Sof(H10Q)=Sof(C108)=Sof(H10R)=Sof(H10S)=Sof(H10T)=Sof(C109)=Sof(H10U)=
 Sof(H10V)=Sof(C110)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C111)=Sof(H11D)=
 Sof(H11E)=Sof(C112)=Sof(H11F)=Sof(H11G)=Sof(H11H)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C29(H29), C34(H34), C37(H37), C40(H40)
7.b Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C103(H10F,H10G), C105(H10K,H10L), C107(H10P,H10Q), C109(H10U,
 H10V), C111(H11D,H11E), C201(H20A,H20B), C203(H20F,H20G), C205(H20K,H20L),
 C207(H20P,H20Q), C209(H20U,H20V), C211(H21D,H21E)
7.c Me refined with riding coordinates:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C35(H35A,H35B,H35C), C36(H36A,
 H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C64(H64A,
 H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C),
 C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C102(H10C,H10D,H10E), C104(H10H,H10I,
 H10J), C106(H10M,H10N,H10O), C108(H10R,H10S,H10T), C110(H11A,H11B,H11C),
 C112(H11F,H11G,H11H), C202(H20C,H20D,H20E), C204(H20H,H20I,H20J), C206(H20M,
 H20N,H20O), C208(H20R,H20S,H20T), C210(H21A,H21B,H21C), C212(H21F,H21G,H21H)
7.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18),
 C44(H44), C46(H46), C48(H48), C58(H58), C60(H60), C62(H62), C121(H121),
 C122(H122), C123(H123), C124(H124), C125(H125), C221(H221), C222(H222),
 C223(H223), C224(H224), C225(H225)
7.e Fitted pentagon refined as free rotating group:
 C121(C122,C123,C124,C125), C221(C222,C223,C224,C225)
;
_shelx_res_checksum              74299
_shelx_fab_checksum              41456
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id Tb-Por
_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 1.909
_oxdiff_exptl_absorpt_empirical_full_min 0.399