Synthesis, Structural Characterization and Rigidity Dependent Dual Luminescence Behavior of High-Energy Phosphorescent Zinc(II) Cyclic (Alkyl)(Amino)carbene Complexes
Mitra, Mousree; Mrózek, Ondřej; Belyaev, Andrey; Janiak, Lars; Marian, Christel Maria; Steffen, Andreas; Dalton Transactions  (2026) –; doi:10.1039/D6DT00177G

data_7720624
_publ_section_title
;
 Synthesis, structural characterization and rigidity dependent dual
 phosphorescence behavior of high-energy phosphorescent zinc(II) cyclic
 (alkyl)(amino)carbene complexes.
;
_journal_issue                   14
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5519
_journal_page_last               5528
_journal_paper_doi               10.1039/d6dt00177g
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C88 H140 Br6 N4 Zn4, 2(B C24 F20), C5 H12'
_chemical_formula_sum            'C141 H152 B2 Br6 F40 N4 Zn4'
_chemical_formula_weight         3425.22
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2025-05-27
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6380)
;
_audit_update_record
;
2025-05-27 deposited with the CCDC.	2026-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.4042(6)
_cell_length_b                   29.9585(6)
_cell_length_c                   47.0638(12)
_cell_measurement_reflns_used    9651
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      29.04
_cell_measurement_theta_min      2.42
_cell_volume                     28769.1(13)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 HPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'CMOS Photon 100'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 VENTURE dual wavelength Mo/Cu'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0777
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       61
_diffrn_reflns_limit_l_min       -61
_diffrn_reflns_number            240312
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         2.111
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.428
_exptl_absorpt_correction_T_max  0.808
_exptl_absorpt_correction_T_min  0.654
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   'SADABS 2016'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.582
_exptl_crystal_description       block
_exptl_crystal_F_000             13808
_exptl_crystal_size_max          0.078
_exptl_crystal_size_mid          0.032
_exptl_crystal_size_min          0.011
_refine_diff_density_max         2.776
_refine_diff_density_min         -1.679
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1796
_refine_ls_number_reflns         33002
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0872
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0612P)^2^+97.8871P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1292
_refine_ls_wR_factor_ref         0.1452
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23538
_reflns_number_total             33002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00177g2.cif
_cod_data_source_block           9
_cod_depositor_comments
'Adding full bibliography for 7720617--7720624.cif.'
_cod_database_code               7720624
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.833
_diffrn_ambient_temperature_device 'Oxford Cryostream 800'
_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
 C137-C138 = C138-C139 = C139-C140 = C140-C141
 1.52 with sigma of 0.02
 C137-C139 = C138-C140 = C139-C141
 2.54 with sigma of 0.04
 C137-C138 \\sim C138-C139 \\sim C139-C140 \\sim C140-C141
 with sigma of 0.02
 C137-C139 \\sim C139-C141 \\sim C138-C140
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C137 \\sim C138 \\sim C139 \\sim C140 \\sim C141: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Uanis(C141) \\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C139) \\sim Ueq,
Uanis(C138) \\sim Ueq, Uanis(C137) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C137) \\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C139) \\sim Ueq,
Uanis(C140) \\sim Ueq, Uanis(C141) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.01
Uanis(C5) = Uanis(C10)
Uanis(C54) = Uanis(C55)
4. Rigid body (RIGU) restrains
 C137, C138, C139, C140, C141
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C20(H20), C23(H23), C41(H41), C44(H44), C62(H62), C65(H65), C83(H83), C86(H86)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C10(H10A,H10B), C12(H12A,H12B), C27(H27A,H27B), C31(H31A,H31B),
 C33(H33A,H33B), C48(H48A,H48B), C52(H52A,H52B), C54(H54A,H54B), C69(H69A,H69B),
  C71(H71A,H71B), C73(H73A,H73B), C138(H13G,H13H), C139(H13I,H13J), C140(H14A,
 H14B)
5.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C18(H18), C37(H37), C38(H38), C39(H39), C58(H58),
 C59(H59), C60(H60), C79(H79), C80(H80), C81(H81)
5.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C),
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C34(H34A,
 H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C53(H53A,H53B,
 H53C), C55(H55A,H55B,H55C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C),
 C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C84(H84A,H84B,H84C), C85(H85A,H85B,
 H85C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C137(H13D,H13E,H13F),
 C141(H14C,H14D,H14E)
;
_olex2_submission_special_instructions 'No special instructions were received'