Tuning Electronic Structure, Redox, and Photophysical Properties in Asymmetric NIR-Absorbing Organometallic BODIPYs.
Zatsikha, Yuriy V.; Maligaspe, Eranda; Purchel, Anatolii A.; Didukh, Natalia O.; Wang, Yefeng; Kovtun, Yuriy P.; Blank, David A.; Nemykin, Victor N.; Inorganic chemistry 54 (2015) 7915–7928; doi:10.1021/acs.inorgchem.5b00992

data_4344033
_publ_section_related_literature
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_publ_section_title
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 Tuning Electronic Structure, Redox, and Photophysical Properties in
 Asymmetric NIR-Absorbing Organometallic BODIPYs.
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_journal_issue                   16
_journal_name_full               'Inorganic chemistry'
_journal_page_first              7915
_journal_page_last               7928
_journal_paper_doi               10.1021/acs.inorgchem.5b00992
_journal_volume                  54
_journal_year                    2015
_chemical_formula_moiety         'C43 H37.50 B1 F2 Fe1 N3 O3'
_chemical_formula_sum            'C43 H37.5 B F2 Fe N3 O3'
_chemical_formula_weight         748.94
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             15-03-26
_audit_creation_method           CRYSTALS_ver_14.40
_cell_angle_alpha                103.130(7)
_cell_angle_beta                 94.420(7)
_cell_angle_gamma                91.117(6)
_cell_formula_units_Z            4
_cell_length_a                   13.5752(2)
_cell_length_b                   15.8246(2)
_cell_length_c                   18.0956(12)
_cell_measurement_reflns_used    44392
_cell_measurement_temperature    123
_cell_measurement_theta_max      65
_cell_measurement_theta_min      8
_cell_volume                     3771.7(3)
_computing_cell_refinement       'USER DEFINED CELL REFINEMENT'
_computing_data_collection       'USER DEFINED DATA COLLECTION'
_computing_data_reduction        'USER DEFINED DATA REDUCTION'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SHELXS 86 (Sheldrick, 1986)'
_diffrn_ambient_temperature      123
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device       Serial
_diffrn_measurement_device_type  Unknown
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.060
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            44392
_diffrn_reflns_theta_full        41.649
_diffrn_reflns_theta_max         65.077
_diffrn_reflns_theta_min         2.516
_diffrn_standards_decay_%        0.00
_diffrn_standards_interval_time  8
_diffrn_standards_number         44392
_exptl_absorpt_coefficient_mu    3.644
_exptl_absorpt_correction_T_max  0.72
_exptl_absorpt_correction_T_min  0.49
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1558
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.090
_refine_diff_density_max         1.40
_refine_diff_density_min         -1.10
_refine_ls_extinction_method     None
_refine_ls_goodness_of_fit_ref   0.9457
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     949
_refine_ls_number_reflns         12566
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.1701
_refine_ls_R_factor_gt           0.0997
_refine_ls_shift/su_max          0.0069121
_refine_ls_shift/su_mean         0.0011184
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 36.2 47.6 13.5 
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_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.2496
_refine_ls_wR_factor_gt          0.1802
_refine_ls_wR_factor_ref         0.2493
_reflns_limit_h_max              15
_reflns_limit_h_min              -15
_reflns_limit_k_max              18
_reflns_limit_k_min              -18
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                6278
_reflns_number_total             12637
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00
_oxford_refine_ls_r_factor_ref   0.1700
_oxford_refine_ls_scale          0.4121(6)
_oxford_reflns_number_all        12567
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_oxford_structure_analysis_title '_07282013-1'
_cod_data_source_file            ic5b00992_si_002.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 4344032--4344035.cif.'
_cod_original_sg_symbol_H-M      'P -1 '
_cod_original_formula_sum        'C43 H37.50 B1 F2 Fe1 N3 O3'
_cod_database_code               4344033
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S 
CONTINUE C(1,U'S) UNTIL C(84) 
CONTINUE FE(1,U'S) UNTIL N(6) 
RIDE C   (   2,X'S) H   (  21,X'S) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) 
RIDE C   (   8,X'S) H   (  81,X'S) 
RIDE C   (   9,X'S) H   (  91,X'S) 
RIDE C   (  10,X'S) H   ( 101,X'S) 
RIDE C   (  11,X'S) H   ( 111,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) H   ( 182,X'S) 
RIDE C   (  19,X'S) H   ( 193,X'S) H   ( 192,X'S) H   ( 191,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) 
RIDE C   (  22,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) H   ( 402,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) H   ( 412,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) H   ( 422,X'S) 
RIDE C   (  43,X'S) H   ( 433,X'S) H   ( 432,X'S) H   ( 431,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) 
RIDE C   (  46,X'S) H   ( 461,X'S) 
RIDE C   (  47,X'S) H   ( 471,X'S) 
RIDE C   (  48,X'S) H   ( 481,X'S) 
RIDE C   (  49,X'S) H   ( 491,X'S) 
RIDE C   (  50,X'S) H   ( 501,X'S) 
RIDE C   (  51,X'S) H   ( 511,X'S) 
RIDE C   (  52,X'S) H   ( 521,X'S) 
RIDE C   (  53,X'S) H   ( 531,X'S) 
RIDE C   (  54,X'S) H   ( 541,X'S) 
RIDE C   (  55,X'S) H   ( 551,X'S) 
RIDE C   (  61,X'S) H   ( 611,X'S) H   ( 612,X'S) 
RIDE C   (  62,X'S) H   ( 623,X'S) H   ( 622,X'S) H   ( 621,X'S) 
RIDE C   (  64,X'S) H   ( 641,X'S) 
RIDE C   (  65,X'S) H   ( 651,X'S) 
RIDE C   (  66,X'S) H   ( 661,X'S) 
RIDE C   (  67,X'S) H   ( 671,X'S) 
RIDE C   (  68,X'S) H   ( 681,X'S) 
RIDE C   (  69,X'S) H   ( 691,X'S) 
RIDE C   (  74,X'S) H   ( 741,X'S) 
RIDE C   (  75,X'S) H   ( 751,X'S) 
RIDE C   (  78,X'S) H   ( 781,X'S) 
RIDE C   (  79,X'S) H   ( 791,X'S) 
RIDE C   (  80,X'S) H   ( 801,X'S) 
RIDE C   (  81,X'S) H   ( 811,X'S) 
RIDE C   (  82,X'S) H   ( 821,X'S) 
RIDE C   (  83,X'S) H   ( 831,X'S) H   ( 832,X'S) 
RIDE C   (  84,X'S) H   ( 841,X'S) 
RIDE C   (  85,X'S) H   ( 851,X'S) H   ( 852,X'S) 
RIDE C   (  86,X'S) H   ( 861,X'S) H   ( 862,X'S) H   ( 863,X'S) 
RIDE C   (  87,X'S) H   ( 871,X'S) H   ( 872,X'S) 
RIDE C   (  88,X'S) H   ( 881,X'S) H   ( 882,X'S) H   ( 883,X'S) 
END                                                                             
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_iucr_refine_instruction_details_restraints
;
DIST 1.54 , 0.01 = C(40) TO C(41) 
DIST 1.54 , 0.01 = C(41) TO C(42) 
DIST 1.54 , 0.01 = C(42) TO C(43) 
DIST 1.54 , 0.01 = C(83) TO C(84) 
DIST 1.54 , 0.01 = C(84) TO C(85) 
DIST 1.54 , 0.01 = C(85) TO C(86) 
DIST 1.54 , 0.01 = C(87) TO C(88) 
DIST 1.54 , 0.01 = C(87) TO C(84) 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
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