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_1550073
_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         'C156 H212 Co2 N8 O18 P6 Si2 Tb2'
_chemical_formula_sum            'C156 H212 Co2 N8 O18 P6 Si2 Tb2'
_chemical_formula_weight         3165.02
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-06-14
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.06.07 svn.r3419 for OlexSys, GUI svn.r5353)
;
_audit_update_record
;
2017-07-27 deposited with the CCDC.
2018-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                75.0610(10)
_cell_angle_beta                 86.2080(10)
_cell_angle_gamma                71.1390(10)
_cell_formula_units_Z            1
_cell_length_a                   10.30820(10)
_cell_length_b                   14.6723(2)
_cell_length_c                   27.9524(5)
_cell_measurement_reflns_used    38803
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.2210
_cell_measurement_theta_min      2.2050
_cell_volume                     3864.76(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9g (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9g (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      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku HG Saturn724+ (2x2 bin mode)'
_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   -109.00  21.00   1.00   35.00    --  -19.60 -72.00-120.00  130
  2  \w   -109.00  21.00   1.00   35.00    --  -19.60 -72.00   0.00  130
  3  \w   -109.00  21.00   1.00   35.00    --  -19.60 -72.00  90.00  130
  4  \w    -58.00  70.00   1.00   35.00    --  -19.60  57.00   0.00  128
  5  \w    -58.00  70.00   1.00   35.00    --  -19.60  57.00 -90.00  128
  6  \w   -109.00  19.00   1.00   35.00    --  -19.60 -57.00 150.00  128
  7  \w    -60.00  70.00   1.00   35.00    --  -19.60  72.00-120.00  130
  8  \w    -60.00   1.00   1.00   35.00    --  -19.60  72.00 150.00   61
  9  \w    -58.00  70.00   1.00   35.00    --  -19.60  57.00 120.00  128
;
_diffrn_measurement_device       'four-circle \k goniometer'
_diffrn_measurement_device_type
'Rigaku FRE+ equipped with HF Varimax confocal mirrors and an AFC12 goniometer and HG Saturn 724+ 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      -0.0013722000
_diffrn_orient_matrix_UB_12      0.0501913000
_diffrn_orient_matrix_UB_13      -0.0047937000
_diffrn_orient_matrix_UB_21      -0.0050128000
_diffrn_orient_matrix_UB_22      -0.0027773000
_diffrn_orient_matrix_UB_23      0.0257346000
_diffrn_orient_matrix_UB_31      0.0725401000
_diffrn_orient_matrix_UB_32      -0.0160456000
_diffrn_orient_matrix_UB_33      0.0021833000
_diffrn_radiation_collimation    0.2
_diffrn_radiation_monochromator  'Confocal mirrors, HF 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  0.0515
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            85977
_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         27.486
_diffrn_reflns_theta_min         2.207
_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    1.257
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71617
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       plate
_exptl_crystal_F_000             1650
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of ethanol and DCM by ---'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.043
_refine_diff_density_min         -2.319
_refine_diff_density_rms         0.121
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.278
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1197
_refine_ls_number_reflns         17755
_refine_ls_number_restraints     2917
_refine_ls_restrained_S_all      1.235
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0625
_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/[\s^2^(Fo^2^)+(0.0216P)^2^+18.4376P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1302
_refine_ls_wR_factor_ref         0.1316
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16997
_reflns_number_total             17755
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03762k2.cif
_cod_data_source_block           P2Tb2
_cod_depositor_comments
'Adding full bibliography for 1550065--1550077.cif.'
_cod_database_code               1550073
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C156 H212 Co2 N8 O18 P6 Si2 Tb2'
_chemical_oxdiff_usercomment     Tb-Por-dimer
_reflns_odcompleteness_completeness 99.94
_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
 C52-C58 \\sim C52-C58B
 with sigma of 0.02
 P101-O105 \\sim P201-O204 \\sim P101-O104 \\sim P203-O209 \\sim P203-O208
\\sim P103-O109 \\sim P103-
 O108 \\sim P202-O207 \\sim P202-O206 \\sim P102-O107 \\sim P102-O106 \\sim
P201-O205
 with sigma of 0.02
 O205-C203 \\sim O106-C105 \\sim O107-C107 \\sim O206-C205 \\sim O207-C207
\\sim O108-C109 \\sim O109-
 C111 \\sim O208-C209 \\sim O209-C211 \\sim O104-C101 \\sim O105-C103 \\sim
O204-C201
 with sigma of 0.02
 O205-C204 \\sim O106-C106 \\sim O107-C108 \\sim O206-C206 \\sim O207-C208
\\sim O108-C110 \\sim O109-
 C112 \\sim O208-C210 \\sim O209-C212 \\sim O104-C102 \\sim O105-C104 \\sim
O204-C202
 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
Uanis(P201) = Uanis(O205)
Uanis(C50) = Uanis(C51)
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
{C58, C59, C60, C61} sigma for 1-2: 0.02, 1-3: 0.04
as
{C58B, C59B, C60B, C61B}
{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(C58B)=Sof(C59B)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60B)=Sof(H60D)=
 Sof(H60E)=Sof(H60F)=Sof(C61B)=Sof(H61D)=Sof(H61E)=Sof(H61F)=1-FVAR(1)
 Sof(C58)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60)=Sof(H60A)=Sof(H60B)=
 Sof(H60C)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(H61C)=FVAR(1)
 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(2)
 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(2)
 Sof(Co1A)=1-FVAR(3)
 Sof(Co1)=FVAR(3)
 Sof(C221)=Sof(H221)=Sof(C222)=Sof(H222)=Sof(C223)=Sof(H223)=Sof(C224)=
 Sof(H224)=Sof(C225)=Sof(H225)=1-FVAR(4)
 Sof(C121)=Sof(H121)=Sof(C122)=Sof(H122)=Sof(C123)=Sof(H123)=Sof(C124)=
 Sof(H124)=Sof(C125)=Sof(H125)=FVAR(4)
 Sof(Tb2)=1-FVAR(5)
 Sof(Tb1)=FVAR(5)
7.a Ternary CH refined with riding coordinates:
 C25(H25), C28(H28), C31(H31), C222(H222)
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 Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18),
 C35(H35), C37(H37), C39(H39), C49(H49), C51(H51), C53(H53), C121(H121),
 C122(H122), C123(H123), C124(H124), C125(H125), C221(H221), C223(H223),
 C224(H224), C225(H225)
7.d Fitted pentagon refined as free rotating group:
 C121(C122,C123,C124,C125), C221(C222,C223,C224,C225)
7.e Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,
 H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C),
 C102(H10C,H10D,H10E), C104(H10H,H10I,H10J), C106(H10M,H10N,H10O), C108(H10R,
 H10S,H10T), C110(H11A,H11B,H11C), C112(H11F,H11G,H11H), C59B(H59D,H59E,H59F),
 C60B(H60D,H60E,H60F), C61B(H61D,H61E,H61F), C202(H20C,H20D,H20E), C204(H20H,
 H20I,H20J), C206(H20M,H20N,H20O), C208(H20R,H20S,H20T), C210(H21A,H21B,H21C),
 C212(H21F,H21G,H21H)
;
_shelx_res_checksum              69232
_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-dimer
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.764
_oxdiff_exptl_absorpt_empirical_full_min 0.694