Stable luminescent iridium(iii) complexes with bis(N-heterocyclic carbene) ligands: photo-stability, excited state properties, visible-light-driven radical cyclization and CO2reduction, and cellular imaging
Yang, Chen; Mehmood, Faisal; Lam, Tsz Lung; Chan, Sharon Lai-Fung; Wu, Yuan; Yeung, Chi-Shun; Guan, Xiangguo; Li, Kai; Chung, Clive Yik-Sham; Zhou, Cong-Ying; Zou, Taotao; Che, Chi-Ming; Chem. Sci. 7 (2016) 3123–; doi:10.1039/C5SC04458H

data_1542301
_publ_section_title
;
 Stable luminescent iridium(iii) complexes with bis(N-heterocyclic
 carbene) ligands: photo-stability, excited state properties,
 visible-light-driven radical cyclization and CO2reduction, and cellular
 imaging
;
_journal_issue                   5
_journal_name_full               'Chem. Sci.'
_journal_page_first              3123
_journal_paper_doi               10.1039/C5SC04458H
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C41 H40 Ir N6 S2, C F3 O3 S'
_chemical_formula_sum            'C42 H40 F3 Ir N6 O3 S3'
_chemical_formula_weight         1022.18
_chemical_name_systematic        '[cis-(Hbta)2Ir(dib)]OTf'
_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     direct
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/cc1jyfyv
_audit_creation_date             2015-06-03
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-09-29 deposited with the CCDC.
2016-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                67.0480(19)
_cell_angle_beta                 67.5521(17)
_cell_angle_gamma                82.559(2)
_cell_formula_units_Z            4
_cell_length_a                   15.8141(6)
_cell_length_b                   16.3895(6)
_cell_length_c                   18.8888(7)
_cell_measurement_reflns_used    9191
_cell_measurement_temperature    100
_cell_measurement_theta_max      54.10
_cell_measurement_theta_min      3.02
_cell_volume                     4165.4(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0819
_diffrn_reflns_av_unetI/netI     0.0759
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            50514
_diffrn_reflns_theta_full        54.43
_diffrn_reflns_theta_max         54.43
_diffrn_reflns_theta_min         2.73
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.120
_exptl_absorpt_correction_T_max  0.7507
_exptl_absorpt_correction_T_min  0.5780
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1064 before and 0.0799 after correction.
The Ratio of minimum to maximum transmission is 0.7699.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.630
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2040
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl3/Et2O'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.03
_refine_diff_density_max         9.706
_refine_diff_density_min         -4.684
_refine_diff_density_rms         0.274
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     996
_refine_ls_number_reflns         10044
_refine_ls_number_restraints     828
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.2365
_refine_ls_R_factor_gt           0.1713
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1623P)^2^+353.9409P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3922
_refine_ls_wR_factor_ref         0.4436
_reflns_number_gt                6324
_reflns_number_total             10044
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5sc04458h2.cif
_cod_data_source_block           david160_0m-p-1
_cod_depositor_comments
'Adding full bibliography for 1542299--1542302.cif.'
_cod_database_code               1542301
_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
 S6-O6 = S6-O5 = S6-O4
 1.4 with sigma of 0.02
 F5-C84 = F4-C84 = F6-C84
 1.33 with sigma of 0.02
 C78-C77 = C76-C75 = C77-C76 = C82-C81 = C80-C79 = C81-C80
 1.53 with sigma of 0.02
 F4-F5
 1.96 with sigma of 0.04
 F5-F6
 1.96 with sigma of 0.04
 F4-F6
 1.96 with sigma of 0.04
 O5-O4
 2.45 with sigma of 0.04
 O5-O6
 2.45 with sigma of 0.04
 O4-O6
 2.45 with sigma of 0.04
 C84-O6
 2.44 with sigma of 0.04
 C84-O5
 2.44 with sigma of 0.04
 C84-O4
 2.44 with sigma of 0.04
 F6-S6
 2.6 with sigma of 0.04
 F5-S6
 2.6 with sigma of 0.04
 F4-S6
 2.6 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(F5) \\sim Ueq, Uanis(F6) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(F4) \\sim
Ueq, Uanis(S6) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O6)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C38(H38A,H38B), C71(H71A,H71B), C80(H80A,H80B), C79(H79A,
 H79B), C81(H81A,H81B), C39(H39A,H39B), C34(H34A,H34B), C35(H35A,H35B),
 C36(H36A,H36B), C75(H75A,H75B), C40(H40A,H40B), C76(H76A,H76B), C77(H77A,H77B)
4.b Aromatic/amide H refined with riding coordinates:
 C33(H33), C9(H9), C10(H10), C11(H11), C12(H12), C32(H32), C25(H25), C24(H24),
 C23(H23), C22(H22), C15(H15), C16(H16), C17(H17), C18(H18), C28(H28), C29(H29),
  C74(H74), C73(H73), C52(H52), C43(H43), C53(H53), C50(H50), C70(H70),
 C51(H51), C44(H44), C45(H45), C69(H69), C59(H59), C3(H3), C2(H2), C5(H5),
 C4(H4), C56(H56), C63(H63), C64(H64), C57(H57), C66(H66), C65(H65), C58(H58),
 C46(H46)
4.c Fitted hexagon refined as free rotating group:
 C9(C10,C11,C12,C13,C8), C21(C26,C25,C24,C23,C22), C15(C16,C17,C18,C19,C14),
 C3(C2,C1,C6,C5,C4)
4.d Idealised Me refined as rotating group:
 C82(H82A,H82B,H82C), C37(H37A,H37B,H37C), C41(H41A,H41B,H41C), C78(H78A,H78B,
 H78C)
;
_olex2_submission_special_instructions 'No special instructions were received'