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_1550075
_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 Dy N4 O9 P3 Si2'
_chemical_formula_sum            'C87 H127 Co Dy N4 O9 P3 Si2'
_chemical_formula_weight         1743.44
_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             2017-03-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-07-27 deposited with the CCDC.
2018-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                98.3820(10)
_cell_angle_beta                 92.0630(10)
_cell_angle_gamma                97.5590(10)
_cell_formula_units_Z            4
_cell_length_a                   16.1487(3)
_cell_length_b                   19.0993(3)
_cell_length_c                   30.5159(5)
_cell_measurement_reflns_used    46452
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.2660
_cell_measurement_theta_min      2.3650
_cell_volume                     9215.9(3)
_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 0.991
_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   0.50   19.00    --  -19.60 -72.00  60.00  260
  2  \w   -109.00  21.00   0.50   19.00    --  -19.60 -72.00-180.00  260
  3  \w   -109.00  21.00   0.50   19.00    --  -19.60 -72.00 -60.00  260
  4  \w   -109.00  21.00   0.50   19.00    --  -19.60 -72.00 120.00  260
  5  \w    -58.00  70.00   0.50   19.00    --  -19.60  38.00-120.00  256
  6  \w    -58.00  70.00   0.50   19.00    --  -19.60  57.00 -90.00  256
  7  \w    -58.00  70.00   0.50   19.00    --  -19.60  38.00   0.00  256
  8  \w    -60.00  70.00   0.50   19.00    --  -19.60  72.00   0.00  260
  9  \w    -60.00  70.00   0.50   19.00    --  -19.60  72.00 150.00  260
 10  \w    -60.00  70.00   0.50   19.00    --  -19.60  72.00  90.00  260
;
_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      -0.0229165000
_diffrn_orient_matrix_UB_12      -0.0030125000
_diffrn_orient_matrix_UB_13      -0.0206153000
_diffrn_orient_matrix_UB_21      0.0372763000
_diffrn_orient_matrix_UB_22      -0.0030834000
_diffrn_orient_matrix_UB_23      -0.0113008000
_diffrn_orient_matrix_UB_31      -0.0073991000
_diffrn_orient_matrix_UB_32      -0.0376570000
_diffrn_orient_matrix_UB_33      -0.0010239000
_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_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            64909
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.560
_diffrn_reflns_theta_min         2.365
_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    1.116
_exptl_absorpt_correction_T_max  0.964
_exptl_absorpt_correction_T_min  0.817
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale dark blueish green'
_exptl_crystal_colour_modifier   'pale dark blueish'
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       plate
_exptl_crystal_F_000             3660
_exptl_crystal_size_max          0.296
_exptl_crystal_size_mid          0.142
_exptl_crystal_size_min          0.034
_refine_diff_density_max         2.187
_refine_diff_density_min         -2.050
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2124
_refine_ls_number_reflns         64909
_refine_ls_number_restraints     5367
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0530
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0564P)^2^+25.2289P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1236
_refine_ls_wR_factor_ref         0.1267
_reflns_Friedel_coverage         0.000
_reflns_number_gt                57464
_reflns_number_total             64909
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03762k2.cif
_cod_data_source_block           P1Dy
_cod_depositor_comments
'Adding full bibliography for 1550065--1550077.cif.'
_cod_database_code               1550075
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C60 H88 Co Dy N4 O9 P3 Si2 (C16 H21)2'
_chemical_oxdiff_usercomment     Dy-Por
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4440(4)
 0.5560(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C161-C167 \\sim C161-C267
 with sigma of 0.02
 C73-C74 \\sim C73-C74A
 with sigma of 0.02
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. 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(P271) = Uanis(O274) = Uanis(C271) = Uanis(C272)
Uanis(P271) = Uanis(O275) = Uanis(C273) = Uanis(C274)
Uanis(P272) = Uanis(O276) = Uanis(C275) = Uanis(C276)
Uanis(P272) = Uanis(O277) = Uanis(C277) = Uanis(C278)
Uanis(P273) = Uanis(O278) = Uanis(C279) = Uanis(C280)
Uanis(P273) = Uanis(O279) = Uanis(C281) = Uanis(C282)
Uanis(O174) = Uanis(C171) = Uanis(C172)
Uanis(O175) = Uanis(C173) = Uanis(C174)
Uanis(O176) = Uanis(C175) = Uanis(C176)
Uanis(O177) = Uanis(C177) = Uanis(C178)
Uanis(O178) = Uanis(C179) = Uanis(C180)
Uanis(O179) = Uanis(C181) = Uanis(C182)
Uanis(C291) = Uanis(C292) = Uanis(C293) = Uanis(C294) = Uanis(C295)
6. 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
7. Same fragment restrains
{C67, C68, C69, C70} sigma for 1-2: 0.02, 1-3: 0.04
as
{C167, C168, C169, C170}
{C67, C68, C69, C70} sigma for 1-2: 0.02, 1-3: 0.04
as
{C267, C268, C269, C270}
{P171, P172, P173, O171, O172, O173, O174, O175, O176, O177, O178, O179, C171,
C172, C173, C174, C175, C176, C177, C178, C179, C180, C181, C182} sigma for
1-2: 0.02, 1-3: 0.04
as
{P271, P272, P273, O271, O272, O273, O274, O275, O276, O277, O278, O279, C271,
C272, C273, C274, C275, C276, C277, C278, C279, C280, C281, C282}
{C191, C192, C193, C194, C195} sigma for 1-2: 0.02, 1-3: 0.04
as
{C291, C292, C293, C294, C295}
8. Others
 Sof(C267)=Sof(C268)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C269)=Sof(H26D)=
 Sof(H26E)=Sof(H26F)=Sof(C270)=Sof(H27A)=Sof(H27B)=Sof(H27C)=1-FVAR(1)
 Sof(C167)=Sof(C168)=Sof(H16J)=Sof(H16K)=Sof(H16L)=Sof(C169)=Sof(H16M)=
 Sof(H16N)=Sof(H16O)=Sof(C170)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
 Sof(P271)=Sof(P272)=Sof(P273)=Sof(O271)=Sof(O272)=Sof(O273)=Sof(O274)=
 Sof(O275)=Sof(O276)=Sof(O277)=Sof(O278)=Sof(O279)=Sof(C271)=Sof(H27D)=
 Sof(H27E)=Sof(C272)=Sof(H27F)=Sof(H27G)=Sof(H27H)=Sof(C273)=Sof(H27I)=
 Sof(H27J)=Sof(C274)=Sof(H27K)=Sof(H27L)=Sof(H27M)=Sof(C275)=Sof(H27N)=
 Sof(H27O)=Sof(C276)=Sof(H27P)=Sof(H27Q)=Sof(H27R)=Sof(C277)=Sof(H27S)=
 Sof(H27T)=Sof(C278)=Sof(H27U)=Sof(H27V)=Sof(H27W)=Sof(C279)=Sof(H27X)=
 Sof(H27Y)=Sof(C280)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C281)=Sof(H28D)=
 Sof(H28E)=Sof(C282)=Sof(H28F)=Sof(H28G)=Sof(H28H)=1-FVAR(2)
 Sof(P171)=Sof(P172)=Sof(P173)=Sof(O171)=Sof(O172)=Sof(O173)=Sof(O174)=
 Sof(O175)=Sof(O176)=Sof(O177)=Sof(O178)=Sof(O179)=Sof(C171)=Sof(H17D)=
 Sof(H17E)=Sof(C172)=Sof(H17F)=Sof(H17G)=Sof(H17H)=Sof(C173)=Sof(H17I)=
 Sof(H17J)=Sof(C174)=Sof(H17K)=Sof(H17L)=Sof(H17M)=Sof(C175)=Sof(H17N)=
 Sof(H17O)=Sof(C176)=Sof(H17P)=Sof(H17Q)=Sof(H17R)=Sof(C177)=Sof(H17S)=
 Sof(H17T)=Sof(C178)=Sof(H17U)=Sof(H17V)=Sof(H17W)=Sof(C179)=Sof(H17X)=
 Sof(H17Y)=Sof(C180)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C181)=Sof(H18D)=
 Sof(H18E)=Sof(C182)=Sof(H18F)=Sof(H18G)=Sof(H18H)=FVAR(2)
 Sof(C291)=Sof(H291)=Sof(C292)=Sof(H292)=Sof(C293)=Sof(H293)=Sof(C294)=
 Sof(H294)=Sof(C295)=Sof(H295)=1-FVAR(3)
 Sof(C191)=Sof(H191)=Sof(C192)=Sof(H192)=Sof(C193)=Sof(H193)=Sof(C194)=
 Sof(H194)=Sof(C195)=Sof(H195)=FVAR(3)
 Sof(C75A)=Sof(H75C)=Sof(H75D)=Sof(C76A)=Sof(H76D)=Sof(H76E)=Sof(H76F)=1-FVAR(4)
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(4)
 Sof(H73C)=Sof(H73D)=Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=1-FVAR(5)
 Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=FVAR(5)
9.a Ternary CH refined with riding coordinates:
 C123(H123), C126(H126), C129(H129), C134(H134), C137(H137), C140(H140),
 C23(H23), C26(H26), C29(H29), C34(H34), C37(H37), C40(H40), C291(H291),
 C292(H292)
9.b Secondary CH2 refined with riding coordinates:
 C171(H17D,H17E), C173(H17I,H17J), C175(H17N,H17O), C177(H17S,H17T), C179(H17X,
 H17Y), C181(H18D,H18E), C271(H27D,H27E), C273(H27I,H27J), C275(H27N,H27O),
 C277(H27S,H27T), C279(H27X,H27Y), C281(H28D,H28E), C71(H71A,H71B), C73(H73A,
 H73B), C73(H73C,H73D), C75(H75A,H75B), C77(H77A,H77B), C79(H79A,H79B),
 C81(H81A,H81B), C75A(H75C,H75D)
9.c Aromatic/amide H refined with riding coordinates:
 C102(H102), C103(H103), C107(H107), C108(H108), C112(H112), C113(H113),
 C117(H117), C118(H118), C144(H144), C146(H146), C148(H148), C158(H158),
 C160(H160), C162(H162), C191(H191), C192(H192), C193(H193), C194(H194),
 C195(H195), 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), C91(H91),
  C92(H92), C93(H93), C94(H94), C95(H95), C293(H293), C294(H294), C295(H295)
9.d Idealised Me refined as rotating group:
 C124(H12A,H12B,H12C), C125(H12D,H12E,H12F), C127(H12G,H12H,H12I), C128(H12J,
 H12K,H12L), C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C135(H13G,H13H,H13I),
 C136(H13J,H13K,H13L), C138(H13M,H13N,H13O), C139(H13P,H13Q,H13R), C141(H14A,
 H14B,H14C), C142(H14D,H14E,H14F), C150(H15A,H15B,H15C), C151(H15D,H15E,H15F),
 C152(H15G,H15H,H15I), C154(H15J,H15K,H15L), C155(H15M,H15N,H15O), C156(H15P,
 H15Q,H15R), C164(H16A,H16B,H16C), C165(H16D,H16E,H16F), C166(H16G,H16H,H16I),
 C168(H16J,H16K,H16L), C169(H16M,H16N,H16O), C170(H17A,H17B,H17C), C172(H17F,
 H17G,H17H), C174(H17K,H17L,H17M), C176(H17P,H17Q,H17R), C178(H17U,H17V,H17W),
 C180(H18A,H18B,H18C), C182(H18F,H18G,H18H), C268(H26A,H26B,H26C), C269(H26D,
 H26E,H26F), C270(H27A,H27B,H27C), C272(H27F,H27G,H27H), C274(H27K,H27L,H27M),
 C276(H27P,H27Q,H27R), C278(H27U,H27V,H27W), C280(H28A,H28B,H28C), C282(H28F,
 H28G,H28H), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27Z,H,HA), C28(H28I,
 H28J,H28K), 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), C72(H72A,H72B,H72C), C76(H76A,
 H76B,H76C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C82(H82A,H82B,H82C),
 C76A(H76D,H76E,H76F), C74(H74A,H74B,H74C), C74A(H74D,H74E,H74F)
;
_shelx_res_checksum              22993
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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 1.789
_oxdiff_exptl_absorpt_empirical_full_min 0.585
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -179.9960\% 
 around [1.00 -0.00 -0.00] (reciprocal) or [0.99 0.12 0.03] (direct)
;