Luminescent CuI complexes have emerged as promising substitutes for phosphorescent emitters based on Ir, Pt and Os due to their abundance and low cost. The title heteroleptic cuprous complex, [9,9-dimethyl-4,5-bis(diphenylphosphanyl)-9H-xanthene-κ2P,P](2-methylquinolin-8-ol-κ2N,O)copper(I) hexafluorophosphate, [Cu(C10H9NO)(C39H32OP2)]PF6, conventionally abbreviated as [Cu(Xantphos)(8-HOXQ)]PF6, where Xantphos is the chelating diphosphine ligand 9,9-dimethyl-4,5-bis(diphenylphosphanyl)-9H-xanthene and 8-HOXQ is the N,O-chelating ligand 2-methylquinolin-8-ol that remains protonated at the hydroxy O atom, is described. In this complex, the asymmetric unit consists of a hexafluorophosphate anion and a whole mononuclear cation, where the CuI atom is coordinated by two P atoms from the Xantphos ligand and by the N and O atoms from the 8-HOXQ ligand, giving rise to a tetrahedral CuP2NO coordination geometry. The electronic absorption and photoluminescence properties of this complex have been studied on as-synthesized samples, whose purity had been determined by powder X-ray diffraction. In the detailed TD–DFT (time-dependent density functional theory) studies, the yellow emission appears to be derived from the inter-ligand charge transfer and metal-to-ligand charge transfer (M+L′)→LCT excited state (LCT is ligand charge transfer).
Supporting information
CCDC reference: 1537504
Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
[9,9-Dimethyl-4,5-bis(diphenylphosphanyl)-9
H-xanthene-
κ2P,
P](2-methylquinolin-8-ol-
κ2N,
O)copper(I)
hexafluorophosphate
top
Crystal data top
[Cu(C10H9NO)(C39H32OP2)]PF6 | F(000) = 1944 |
Mr = 946.28 | Dx = 1.408 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.5376 (6) Å | Cell parameters from 3939 reflections |
b = 21.5025 (14) Å | θ = 3.0–29.5° |
c = 19.9462 (19) Å | µ = 0.66 mm−1 |
β = 99.079 (7)° | T = 273 K |
V = 4462.9 (6) Å3 | Plate, brown–yellow |
Z = 4 | 0.49 × 0.4 × 0.29 mm |
Data collection top
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 10570 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 6277 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 10.3592 pixels mm-1 | θmax = 29.6°, θmin = 3.0° |
ω scans | h = −10→14 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −28→18 |
Tmin = 0.758, Tmax = 1.000 | l = −25→20 |
20841 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.198 | w = 1/[σ2(Fo2) + (0.087P)2 + 3.132P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
10570 reflections | Δρmax = 0.71 e Å−3 |
563 parameters | Δρmin = −0.64 e Å−3 |
3 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.35844 (4) | 0.24536 (2) | 0.48474 (2) | 0.04201 (16) | |
P1 | 0.18848 (9) | 0.20212 (4) | 0.52757 (5) | 0.0399 (2) | |
P2 | 0.31549 (8) | 0.32818 (5) | 0.41537 (5) | 0.0390 (2) | |
O1 | 0.4361 (3) | 0.16039 (15) | 0.43613 (17) | 0.0664 (9) | |
H1 | 0.4187 | 0.1374 | 0.4011 | 0.100* | |
O2 | 0.1577 (2) | 0.33440 (12) | 0.51944 (12) | 0.0439 (6) | |
N1 | 0.5361 (3) | 0.23085 (17) | 0.54151 (17) | 0.0501 (8) | |
C1 | 0.5897 (3) | 0.1733 (2) | 0.5344 (2) | 0.0517 (10) | |
C2 | 0.5345 (4) | 0.1345 (2) | 0.4804 (2) | 0.0549 (11) | |
C3 | 0.5800 (5) | 0.0765 (2) | 0.4733 (3) | 0.0757 (14) | |
H3 | 0.5437 | 0.0514 | 0.4374 | 0.091* | |
C4 | 0.6839 (6) | 0.0543 (3) | 0.5214 (4) | 0.0945 (19) | |
H4 | 0.7135 | 0.0139 | 0.5177 | 0.113* | |
C5 | 0.7401 (5) | 0.0909 (3) | 0.5724 (3) | 0.0851 (17) | |
H5 | 0.8092 | 0.0758 | 0.6027 | 0.102* | |
C6 | 0.6961 (4) | 0.1514 (3) | 0.5802 (3) | 0.0677 (14) | |
C7 | 0.7517 (5) | 0.1927 (3) | 0.6313 (3) | 0.0818 (16) | |
H7 | 0.8228 | 0.1803 | 0.6621 | 0.098* | |
C8 | 0.7018 (5) | 0.2506 (3) | 0.6357 (3) | 0.0812 (17) | |
H8 | 0.7404 | 0.2785 | 0.6683 | 0.097* | |
C9 | 0.5915 (4) | 0.2680 (2) | 0.5904 (2) | 0.0595 (11) | |
C10 | 0.5292 (6) | 0.3297 (2) | 0.5979 (3) | 0.0898 (18) | |
H10A | 0.5196 | 0.3516 | 0.5554 | 0.135* | |
H10B | 0.5819 | 0.3537 | 0.6321 | 0.135* | |
H10C | 0.4462 | 0.3234 | 0.6108 | 0.135* | |
C11 | 0.2076 (4) | 0.12609 (18) | 0.5690 (2) | 0.0454 (9) | |
C12 | 0.3279 (4) | 0.1089 (2) | 0.6028 (2) | 0.0519 (10) | |
H12 | 0.3971 | 0.1358 | 0.6031 | 0.062* | |
C13 | 0.3460 (5) | 0.0525 (2) | 0.6356 (2) | 0.0658 (13) | |
H13 | 0.4270 | 0.0414 | 0.6581 | 0.079* | |
C14 | 0.2442 (6) | 0.0129 (2) | 0.6352 (3) | 0.0725 (14) | |
H14 | 0.2562 | −0.0252 | 0.6574 | 0.087* | |
C15 | 0.1252 (5) | 0.0289 (2) | 0.6025 (3) | 0.0743 (14) | |
H15 | 0.0569 | 0.0015 | 0.6022 | 0.089* | |
C16 | 0.1051 (4) | 0.0852 (2) | 0.5698 (2) | 0.0595 (11) | |
H16 | 0.0233 | 0.0959 | 0.5482 | 0.071* | |
C17 | 0.0411 (3) | 0.19129 (18) | 0.4671 (2) | 0.0446 (9) | |
C18 | 0.0448 (4) | 0.1507 (2) | 0.4136 (2) | 0.0560 (11) | |
H18 | 0.1218 | 0.1312 | 0.4091 | 0.067* | |
C19 | −0.0643 (5) | 0.1386 (2) | 0.3666 (3) | 0.0712 (14) | |
H19 | −0.0607 | 0.1110 | 0.3310 | 0.085* | |
C20 | −0.1769 (5) | 0.1677 (3) | 0.3732 (3) | 0.0771 (16) | |
H20 | −0.2502 | 0.1600 | 0.3417 | 0.093* | |
C21 | −0.1830 (4) | 0.2078 (3) | 0.4251 (3) | 0.0757 (15) | |
H21 | −0.2603 | 0.2274 | 0.4287 | 0.091* | |
C22 | −0.0743 (4) | 0.2201 (2) | 0.4731 (2) | 0.0598 (11) | |
H22 | −0.0794 | 0.2474 | 0.5088 | 0.072* | |
C23 | 0.1407 (3) | 0.25128 (17) | 0.59370 (19) | 0.0415 (8) | |
C24 | 0.1136 (4) | 0.2307 (2) | 0.6556 (2) | 0.0535 (10) | |
H24 | 0.1138 | 0.1882 | 0.6645 | 0.064* | |
C25 | 0.0864 (5) | 0.2715 (2) | 0.7042 (2) | 0.0625 (12) | |
H25 | 0.0665 | 0.2565 | 0.7451 | 0.075* | |
C26 | 0.0885 (4) | 0.3351 (2) | 0.6925 (2) | 0.0596 (11) | |
H26 | 0.0722 | 0.3624 | 0.7263 | 0.072* | |
C27 | 0.1144 (4) | 0.35883 (19) | 0.6311 (2) | 0.0477 (9) | |
C28 | 0.1379 (3) | 0.31585 (17) | 0.58318 (19) | 0.0406 (8) | |
C29 | 0.1099 (4) | 0.4276 (2) | 0.6129 (2) | 0.0561 (11) | |
C30 | 0.1478 (7) | 0.4687 (3) | 0.6763 (3) | 0.102 (2) | |
H30A | 0.2355 | 0.4606 | 0.6956 | 0.153* | |
H30B | 0.0929 | 0.4594 | 0.7091 | 0.153* | |
H30C | 0.1385 | 0.5117 | 0.6636 | 0.153* | |
C31 | −0.0285 (4) | 0.4433 (2) | 0.5803 (3) | 0.0793 (16) | |
H31A | −0.0347 | 0.4869 | 0.5699 | 0.119* | |
H31B | −0.0864 | 0.4332 | 0.6113 | 0.119* | |
H31C | −0.0509 | 0.4197 | 0.5392 | 0.119* | |
C32 | 0.1990 (4) | 0.43880 (18) | 0.5609 (2) | 0.0470 (9) | |
C33 | 0.2156 (3) | 0.39230 (16) | 0.51543 (19) | 0.0408 (8) | |
C34 | 0.2892 (3) | 0.39792 (16) | 0.4638 (2) | 0.0398 (8) | |
C35 | 0.3452 (4) | 0.45553 (19) | 0.4563 (2) | 0.0526 (10) | |
H35 | 0.3929 | 0.4619 | 0.4215 | 0.063* | |
C36 | 0.3303 (4) | 0.5034 (2) | 0.5006 (3) | 0.0611 (12) | |
H36 | 0.3680 | 0.5418 | 0.4952 | 0.073* | |
C37 | 0.2607 (4) | 0.4950 (2) | 0.5523 (2) | 0.0583 (11) | |
H37 | 0.2543 | 0.5274 | 0.5824 | 0.070* | |
C38 | 0.4366 (3) | 0.35287 (18) | 0.3645 (2) | 0.0445 (9) | |
C39 | 0.5612 (4) | 0.3338 (2) | 0.3840 (2) | 0.0556 (11) | |
H39 | 0.5819 | 0.3086 | 0.4221 | 0.067* | |
C40 | 0.6559 (4) | 0.3517 (2) | 0.3476 (3) | 0.0668 (13) | |
H40 | 0.7403 | 0.3389 | 0.3615 | 0.080* | |
C41 | 0.6265 (4) | 0.3878 (2) | 0.2918 (3) | 0.0616 (12) | |
H41 | 0.6908 | 0.3993 | 0.2673 | 0.074* | |
C42 | 0.5038 (4) | 0.4077 (2) | 0.2713 (3) | 0.0665 (13) | |
H42 | 0.4843 | 0.4331 | 0.2333 | 0.080* | |
C43 | 0.4083 (4) | 0.3896 (2) | 0.3075 (2) | 0.0597 (12) | |
H43 | 0.3241 | 0.4023 | 0.2932 | 0.072* | |
C44 | 0.1699 (3) | 0.32183 (18) | 0.35321 (19) | 0.0419 (8) | |
C45 | 0.1440 (4) | 0.2647 (2) | 0.3219 (2) | 0.0584 (11) | |
H45 | 0.1991 | 0.2312 | 0.3334 | 0.070* | |
C46 | 0.0346 (5) | 0.2577 (2) | 0.2730 (3) | 0.0719 (14) | |
H46 | 0.0162 | 0.2194 | 0.2521 | 0.086* | |
C47 | −0.0451 (5) | 0.3068 (3) | 0.2557 (3) | 0.0770 (15) | |
H47 | −0.1183 | 0.3018 | 0.2234 | 0.092* | |
C48 | −0.0179 (4) | 0.3633 (3) | 0.2858 (3) | 0.0790 (16) | |
H48 | −0.0718 | 0.3970 | 0.2729 | 0.095* | |
C49 | 0.0874 (4) | 0.3710 (2) | 0.3345 (2) | 0.0600 (12) | |
H49 | 0.1038 | 0.4095 | 0.3552 | 0.072* | |
P3 | 0.27828 (15) | 0.06274 (7) | 0.27776 (8) | 0.0782 (4) | |
F1 | 0.2925 (5) | 0.0686 (3) | 0.3584 (2) | 0.167 (2) | |
F2 | 0.2978 (8) | −0.0060 (3) | 0.2826 (4) | 0.246 (4) | |
F3 | 0.4268 (5) | 0.0636 (3) | 0.2922 (3) | 0.199 (3) | |
F4 | 0.2743 (8) | 0.0649 (5) | 0.2037 (3) | 0.288 (5) | |
F5 | 0.2625 (11) | 0.1297 (3) | 0.2790 (4) | 0.308 (6) | |
F6 | 0.1407 (5) | 0.0530 (5) | 0.2722 (5) | 0.293 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0389 (2) | 0.0410 (3) | 0.0447 (3) | 0.00433 (18) | 0.00251 (19) | 0.0008 (2) |
P1 | 0.0416 (5) | 0.0346 (5) | 0.0438 (6) | 0.0031 (4) | 0.0079 (4) | 0.0018 (4) |
P2 | 0.0375 (5) | 0.0393 (5) | 0.0401 (5) | 0.0031 (4) | 0.0062 (4) | 0.0016 (4) |
O1 | 0.0641 (18) | 0.066 (2) | 0.063 (2) | 0.0211 (16) | −0.0087 (15) | −0.0183 (16) |
O2 | 0.0615 (15) | 0.0358 (15) | 0.0356 (14) | −0.0015 (11) | 0.0114 (12) | −0.0013 (11) |
N1 | 0.0438 (17) | 0.060 (2) | 0.0451 (19) | −0.0009 (15) | 0.0023 (14) | 0.0039 (17) |
C1 | 0.0405 (19) | 0.059 (3) | 0.057 (3) | 0.0065 (18) | 0.0120 (18) | 0.012 (2) |
C2 | 0.050 (2) | 0.056 (3) | 0.060 (3) | 0.0101 (19) | 0.0143 (19) | 0.004 (2) |
C3 | 0.085 (3) | 0.059 (3) | 0.087 (4) | 0.025 (3) | 0.024 (3) | 0.001 (3) |
C4 | 0.090 (4) | 0.083 (4) | 0.116 (5) | 0.040 (3) | 0.030 (4) | 0.026 (4) |
C5 | 0.068 (3) | 0.100 (5) | 0.086 (4) | 0.035 (3) | 0.007 (3) | 0.025 (4) |
C6 | 0.047 (2) | 0.088 (4) | 0.069 (3) | 0.016 (2) | 0.009 (2) | 0.023 (3) |
C7 | 0.054 (3) | 0.115 (5) | 0.069 (4) | 0.014 (3) | −0.009 (2) | 0.016 (3) |
C8 | 0.064 (3) | 0.112 (5) | 0.058 (3) | −0.010 (3) | −0.017 (2) | −0.003 (3) |
C9 | 0.054 (2) | 0.067 (3) | 0.052 (3) | −0.007 (2) | −0.0055 (19) | −0.004 (2) |
C10 | 0.110 (4) | 0.069 (4) | 0.078 (4) | 0.004 (3) | −0.023 (3) | −0.015 (3) |
C11 | 0.053 (2) | 0.034 (2) | 0.049 (2) | 0.0071 (17) | 0.0097 (17) | 0.0002 (17) |
C12 | 0.058 (2) | 0.045 (2) | 0.053 (3) | 0.0091 (18) | 0.0112 (19) | 0.006 (2) |
C13 | 0.080 (3) | 0.056 (3) | 0.059 (3) | 0.024 (2) | 0.006 (2) | 0.005 (2) |
C14 | 0.115 (4) | 0.040 (3) | 0.062 (3) | 0.015 (3) | 0.015 (3) | 0.012 (2) |
C15 | 0.093 (4) | 0.047 (3) | 0.082 (4) | −0.010 (2) | 0.009 (3) | 0.016 (3) |
C16 | 0.064 (3) | 0.049 (3) | 0.066 (3) | −0.003 (2) | 0.011 (2) | 0.006 (2) |
C17 | 0.046 (2) | 0.038 (2) | 0.049 (2) | −0.0022 (16) | 0.0062 (17) | 0.0067 (18) |
C18 | 0.056 (2) | 0.058 (3) | 0.055 (3) | −0.007 (2) | 0.0083 (19) | 0.001 (2) |
C19 | 0.084 (3) | 0.071 (3) | 0.055 (3) | −0.026 (3) | −0.002 (2) | −0.001 (2) |
C20 | 0.066 (3) | 0.080 (4) | 0.076 (4) | −0.015 (3) | −0.016 (3) | 0.020 (3) |
C21 | 0.050 (3) | 0.080 (4) | 0.093 (4) | 0.008 (2) | −0.002 (2) | 0.025 (3) |
C22 | 0.056 (2) | 0.057 (3) | 0.066 (3) | 0.012 (2) | 0.006 (2) | 0.009 (2) |
C23 | 0.0450 (19) | 0.040 (2) | 0.040 (2) | 0.0022 (16) | 0.0075 (15) | 0.0040 (17) |
C24 | 0.067 (3) | 0.047 (2) | 0.048 (2) | 0.006 (2) | 0.015 (2) | 0.010 (2) |
C25 | 0.089 (3) | 0.060 (3) | 0.041 (2) | 0.012 (2) | 0.021 (2) | 0.013 (2) |
C26 | 0.075 (3) | 0.064 (3) | 0.041 (2) | 0.010 (2) | 0.014 (2) | −0.005 (2) |
C27 | 0.055 (2) | 0.047 (2) | 0.041 (2) | 0.0068 (18) | 0.0068 (17) | −0.0019 (18) |
C28 | 0.0455 (19) | 0.039 (2) | 0.037 (2) | 0.0008 (16) | 0.0048 (15) | 0.0010 (16) |
C29 | 0.078 (3) | 0.046 (2) | 0.046 (2) | 0.004 (2) | 0.013 (2) | −0.006 (2) |
C30 | 0.178 (6) | 0.069 (4) | 0.070 (4) | −0.018 (4) | 0.049 (4) | −0.029 (3) |
C31 | 0.075 (3) | 0.072 (3) | 0.098 (4) | 0.032 (3) | 0.033 (3) | 0.022 (3) |
C32 | 0.055 (2) | 0.037 (2) | 0.048 (2) | 0.0037 (17) | 0.0035 (17) | −0.0056 (18) |
C33 | 0.0449 (19) | 0.0312 (19) | 0.044 (2) | 0.0014 (15) | −0.0008 (16) | 0.0013 (16) |
C34 | 0.0367 (17) | 0.035 (2) | 0.046 (2) | 0.0049 (15) | 0.0029 (15) | −0.0009 (16) |
C35 | 0.046 (2) | 0.047 (2) | 0.065 (3) | −0.0036 (18) | 0.0086 (18) | 0.001 (2) |
C36 | 0.058 (2) | 0.038 (2) | 0.087 (4) | −0.0096 (19) | 0.012 (2) | −0.005 (2) |
C37 | 0.066 (3) | 0.040 (2) | 0.066 (3) | −0.0028 (19) | 0.003 (2) | −0.010 (2) |
C38 | 0.046 (2) | 0.041 (2) | 0.048 (2) | 0.0031 (16) | 0.0105 (16) | −0.0032 (18) |
C39 | 0.048 (2) | 0.058 (3) | 0.063 (3) | 0.0124 (19) | 0.0136 (19) | 0.005 (2) |
C40 | 0.045 (2) | 0.073 (3) | 0.086 (4) | 0.003 (2) | 0.022 (2) | −0.001 (3) |
C41 | 0.059 (3) | 0.058 (3) | 0.074 (3) | −0.011 (2) | 0.030 (2) | −0.009 (3) |
C42 | 0.067 (3) | 0.074 (3) | 0.062 (3) | −0.004 (2) | 0.021 (2) | 0.011 (3) |
C43 | 0.047 (2) | 0.073 (3) | 0.060 (3) | 0.001 (2) | 0.0112 (19) | 0.015 (2) |
C44 | 0.0390 (18) | 0.048 (2) | 0.039 (2) | −0.0012 (16) | 0.0081 (15) | 0.0014 (17) |
C45 | 0.069 (3) | 0.053 (3) | 0.051 (3) | −0.004 (2) | 0.000 (2) | 0.004 (2) |
C46 | 0.088 (4) | 0.072 (3) | 0.052 (3) | −0.028 (3) | −0.002 (2) | −0.006 (2) |
C47 | 0.053 (3) | 0.110 (5) | 0.062 (3) | −0.013 (3) | −0.008 (2) | 0.009 (3) |
C48 | 0.054 (3) | 0.099 (4) | 0.077 (4) | 0.023 (3) | −0.012 (2) | −0.004 (3) |
C49 | 0.049 (2) | 0.062 (3) | 0.066 (3) | 0.011 (2) | −0.002 (2) | −0.009 (2) |
P3 | 0.0936 (10) | 0.0697 (10) | 0.0739 (10) | 0.0095 (7) | 0.0213 (8) | −0.0098 (7) |
F1 | 0.202 (5) | 0.200 (5) | 0.099 (3) | 0.000 (4) | 0.026 (3) | −0.026 (3) |
F2 | 0.337 (9) | 0.091 (4) | 0.279 (9) | 0.008 (5) | −0.047 (7) | −0.040 (4) |
F3 | 0.113 (3) | 0.269 (8) | 0.217 (6) | 0.010 (4) | 0.034 (4) | 0.062 (6) |
F4 | 0.297 (8) | 0.502 (14) | 0.071 (3) | 0.181 (9) | 0.046 (4) | 0.042 (6) |
F5 | 0.576 (17) | 0.086 (4) | 0.250 (9) | 0.110 (7) | 0.031 (10) | 0.011 (4) |
F6 | 0.106 (4) | 0.399 (13) | 0.377 (12) | −0.061 (6) | 0.046 (5) | −0.139 (10) |
Geometric parameters (Å, º) top
Cu1—P1 | 2.2989 (10) | C23—C24 | 1.384 (6) |
Cu1—P2 | 2.2569 (11) | C23—C28 | 1.404 (5) |
Cu1—O1 | 2.280 (3) | C24—H24 | 0.9300 |
Cu1—N1 | 2.053 (3) | C24—C25 | 1.371 (6) |
P1—C11 | 1.829 (4) | C25—H25 | 0.9300 |
P1—C17 | 1.825 (4) | C25—C26 | 1.388 (6) |
P1—C23 | 1.822 (4) | C26—H26 | 0.9300 |
P2—C34 | 1.828 (4) | C26—C27 | 1.392 (6) |
P2—C38 | 1.829 (4) | C27—C28 | 1.380 (5) |
P2—C44 | 1.819 (4) | C27—C29 | 1.522 (6) |
O1—H1 | 0.8515 | C29—C30 | 1.543 (7) |
O1—C2 | 1.371 (5) | C29—C31 | 1.538 (6) |
O2—C28 | 1.380 (4) | C29—C32 | 1.523 (6) |
O2—C33 | 1.394 (4) | C30—H30A | 0.9600 |
N1—C1 | 1.376 (5) | C30—H30B | 0.9600 |
N1—C9 | 1.323 (5) | C30—H30C | 0.9600 |
C1—C2 | 1.414 (6) | C31—H31A | 0.9600 |
C1—C6 | 1.410 (6) | C31—H31B | 0.9600 |
C2—C3 | 1.352 (6) | C31—H31C | 0.9600 |
C3—H3 | 0.9300 | C32—C33 | 1.380 (5) |
C3—C4 | 1.419 (8) | C32—C37 | 1.395 (6) |
C4—H4 | 0.9300 | C33—C34 | 1.389 (5) |
C4—C5 | 1.346 (9) | C34—C35 | 1.390 (5) |
C5—H5 | 0.9300 | C35—H35 | 0.9300 |
C5—C6 | 1.398 (8) | C35—C36 | 1.382 (6) |
C6—C7 | 1.407 (8) | C36—H36 | 0.9300 |
C7—H7 | 0.9300 | C36—C37 | 1.368 (6) |
C7—C8 | 1.361 (8) | C37—H37 | 0.9300 |
C8—H8 | 0.9300 | C38—C39 | 1.372 (5) |
C8—C9 | 1.405 (6) | C38—C43 | 1.377 (6) |
C9—C10 | 1.498 (7) | C39—H39 | 0.9300 |
C10—H10A | 0.9600 | C39—C40 | 1.379 (6) |
C10—H10B | 0.9600 | C40—H40 | 0.9300 |
C10—H10C | 0.9600 | C40—C41 | 1.352 (7) |
C11—C12 | 1.388 (5) | C41—H41 | 0.9300 |
C11—C16 | 1.395 (6) | C41—C42 | 1.362 (6) |
C12—H12 | 0.9300 | C42—H42 | 0.9300 |
C12—C13 | 1.377 (6) | C42—C43 | 1.384 (6) |
C13—H13 | 0.9300 | C43—H43 | 0.9300 |
C13—C14 | 1.370 (7) | C44—C45 | 1.386 (6) |
C14—H14 | 0.9300 | C44—C49 | 1.382 (6) |
C14—C15 | 1.363 (7) | C45—H45 | 0.9300 |
C15—H15 | 0.9300 | C45—C46 | 1.396 (6) |
C15—C16 | 1.375 (6) | C46—H46 | 0.9300 |
C16—H16 | 0.9300 | C46—C47 | 1.358 (7) |
C17—C18 | 1.383 (6) | C47—H47 | 0.9300 |
C17—C22 | 1.388 (6) | C47—C48 | 1.366 (8) |
C18—H18 | 0.9300 | C48—H48 | 0.9300 |
C18—C19 | 1.389 (6) | C48—C49 | 1.365 (6) |
C19—H19 | 0.9300 | C49—H49 | 0.9300 |
C19—C20 | 1.367 (7) | P3—F1 | 1.596 (5) |
C20—H20 | 0.9300 | P3—F2 | 1.493 (6) |
C20—C21 | 1.356 (8) | P3—F3 | 1.546 (5) |
C21—H21 | 0.9300 | P3—F4 | 1.472 (5) |
C21—C22 | 1.398 (7) | P3—F5 | 1.449 (6) |
C22—H22 | 0.9300 | P3—F6 | 1.452 (5) |
| | | |
P2—Cu1—P1 | 117.03 (4) | C24—C25—H25 | 120.0 |
P2—Cu1—O1 | 114.98 (9) | C24—C25—C26 | 120.0 (4) |
O1—Cu1—P1 | 100.77 (10) | C26—C25—H25 | 120.0 |
N1—Cu1—P1 | 115.44 (10) | C25—C26—H26 | 119.3 |
N1—Cu1—P2 | 122.36 (10) | C25—C26—C27 | 121.4 (4) |
N1—Cu1—O1 | 75.86 (12) | C27—C26—H26 | 119.3 |
C11—P1—Cu1 | 119.54 (13) | C26—C27—C29 | 124.3 (4) |
C17—P1—Cu1 | 115.93 (13) | C28—C27—C26 | 116.4 (4) |
C17—P1—C11 | 101.92 (17) | C28—C27—C29 | 119.1 (4) |
C23—P1—Cu1 | 110.78 (12) | O2—C28—C23 | 114.9 (3) |
C23—P1—C11 | 102.39 (18) | O2—C28—C27 | 121.0 (3) |
C23—P1—C17 | 104.43 (18) | C27—C28—C23 | 124.1 (4) |
C34—P2—Cu1 | 110.85 (13) | C27—C29—C30 | 111.5 (4) |
C34—P2—C38 | 103.41 (17) | C27—C29—C31 | 107.9 (4) |
C38—P2—Cu1 | 118.62 (13) | C27—C29—C32 | 108.5 (3) |
C44—P2—Cu1 | 115.12 (13) | C31—C29—C30 | 109.1 (4) |
C44—P2—C34 | 103.86 (16) | C32—C29—C30 | 111.1 (4) |
C44—P2—C38 | 103.36 (17) | C32—C29—C31 | 108.8 (4) |
Cu1—O1—H1 | 140.2 | C29—C30—H30A | 109.5 |
C2—O1—Cu1 | 109.7 (3) | C29—C30—H30B | 109.5 |
C2—O1—H1 | 109.7 | C29—C30—H30C | 109.5 |
C28—O2—C33 | 116.2 (3) | H30A—C30—H30B | 109.5 |
C1—N1—Cu1 | 115.7 (3) | H30A—C30—H30C | 109.5 |
C9—N1—Cu1 | 125.0 (3) | H30B—C30—H30C | 109.5 |
C9—N1—C1 | 118.5 (4) | C29—C31—H31A | 109.5 |
N1—C1—C2 | 118.9 (4) | C29—C31—H31B | 109.5 |
N1—C1—C6 | 122.1 (4) | C29—C31—H31C | 109.5 |
C6—C1—C2 | 119.0 (4) | H31A—C31—H31B | 109.5 |
O1—C2—C1 | 115.4 (4) | H31A—C31—H31C | 109.5 |
C3—C2—O1 | 123.5 (4) | H31B—C31—H31C | 109.5 |
C3—C2—C1 | 121.0 (4) | C33—C32—C29 | 119.3 (4) |
C2—C3—H3 | 120.4 | C33—C32—C37 | 115.8 (4) |
C2—C3—C4 | 119.1 (6) | C37—C32—C29 | 124.8 (4) |
C4—C3—H3 | 120.4 | C32—C33—O2 | 120.5 (3) |
C3—C4—H4 | 119.5 | C32—C33—C34 | 124.6 (3) |
C5—C4—C3 | 121.0 (6) | C34—C33—O2 | 114.9 (3) |
C5—C4—H4 | 119.5 | C33—C34—P2 | 118.0 (3) |
C4—C5—H5 | 119.5 | C33—C34—C35 | 116.9 (4) |
C4—C5—C6 | 120.9 (5) | C35—C34—P2 | 124.9 (3) |
C6—C5—H5 | 119.5 | C34—C35—H35 | 119.9 |
C5—C6—C1 | 118.8 (5) | C36—C35—C34 | 120.2 (4) |
C5—C6—C7 | 124.0 (5) | C36—C35—H35 | 119.9 |
C7—C6—C1 | 117.1 (5) | C35—C36—H36 | 119.6 |
C6—C7—H7 | 119.9 | C37—C36—C35 | 120.7 (4) |
C8—C7—C6 | 120.2 (4) | C37—C36—H36 | 119.6 |
C8—C7—H7 | 119.9 | C32—C37—H37 | 119.2 |
C7—C8—H8 | 120.3 | C36—C37—C32 | 121.6 (4) |
C7—C8—C9 | 119.4 (5) | C36—C37—H37 | 119.2 |
C9—C8—H8 | 120.3 | C39—C38—P2 | 118.5 (3) |
N1—C9—C8 | 122.5 (5) | C39—C38—C43 | 118.5 (4) |
N1—C9—C10 | 117.3 (4) | C43—C38—P2 | 123.0 (3) |
C8—C9—C10 | 120.2 (4) | C38—C39—H39 | 119.8 |
C9—C10—H10A | 109.5 | C38—C39—C40 | 120.5 (4) |
C9—C10—H10B | 109.5 | C40—C39—H39 | 119.8 |
C9—C10—H10C | 109.5 | C39—C40—H40 | 119.9 |
H10A—C10—H10B | 109.5 | C41—C40—C39 | 120.2 (4) |
H10A—C10—H10C | 109.5 | C41—C40—H40 | 119.9 |
H10B—C10—H10C | 109.5 | C40—C41—H41 | 119.6 |
C12—C11—P1 | 118.9 (3) | C40—C41—C42 | 120.7 (4) |
C12—C11—C16 | 118.4 (4) | C42—C41—H41 | 119.6 |
C16—C11—P1 | 122.6 (3) | C41—C42—H42 | 120.4 |
C11—C12—H12 | 119.6 | C41—C42—C43 | 119.2 (5) |
C13—C12—C11 | 120.8 (4) | C43—C42—H42 | 120.4 |
C13—C12—H12 | 119.6 | C38—C43—C42 | 120.8 (4) |
C12—C13—H13 | 120.1 | C38—C43—H43 | 119.6 |
C14—C13—C12 | 119.7 (4) | C42—C43—H43 | 119.6 |
C14—C13—H13 | 120.1 | C45—C44—P2 | 117.3 (3) |
C13—C14—H14 | 119.8 | C49—C44—P2 | 123.6 (3) |
C15—C14—C13 | 120.4 (4) | C49—C44—C45 | 119.1 (4) |
C15—C14—H14 | 119.8 | C44—C45—H45 | 120.3 |
C14—C15—H15 | 119.6 | C44—C45—C46 | 119.5 (4) |
C14—C15—C16 | 120.7 (5) | C46—C45—H45 | 120.3 |
C16—C15—H15 | 119.6 | C45—C46—H46 | 119.9 |
C11—C16—H16 | 120.0 | C47—C46—C45 | 120.2 (5) |
C15—C16—C11 | 119.9 (4) | C47—C46—H46 | 119.9 |
C15—C16—H16 | 120.0 | C46—C47—H47 | 119.9 |
C18—C17—P1 | 117.7 (3) | C46—C47—C48 | 120.1 (4) |
C18—C17—C22 | 118.8 (4) | C48—C47—H47 | 119.9 |
C22—C17—P1 | 123.4 (3) | C47—C48—H48 | 119.6 |
C17—C18—H18 | 119.4 | C49—C48—C47 | 120.7 (5) |
C17—C18—C19 | 121.2 (4) | C49—C48—H48 | 119.6 |
C19—C18—H18 | 119.4 | C44—C49—H49 | 119.8 |
C18—C19—H19 | 120.4 | C48—C49—C44 | 120.4 (4) |
C20—C19—C18 | 119.2 (5) | C48—C49—H49 | 119.8 |
C20—C19—H19 | 120.4 | F2—P3—F1 | 91.3 (4) |
C19—C20—H20 | 119.6 | F2—P3—F3 | 82.8 (4) |
C21—C20—C19 | 120.7 (5) | F3—P3—F1 | 83.1 (3) |
C21—C20—H20 | 119.6 | F4—P3—F1 | 172.7 (5) |
C20—C21—H21 | 119.6 | F4—P3—F2 | 94.4 (5) |
C20—C21—C22 | 120.8 (5) | F4—P3—F3 | 93.1 (4) |
C22—C21—H21 | 119.6 | F5—P3—F1 | 84.1 (4) |
C17—C22—C21 | 119.3 (5) | F5—P3—F2 | 175.4 (5) |
C17—C22—H22 | 120.4 | F5—P3—F3 | 95.8 (5) |
C21—C22—H22 | 120.4 | F5—P3—F4 | 90.0 (5) |
C24—C23—P1 | 125.5 (3) | F5—P3—F6 | 91.6 (6) |
C24—C23—C28 | 116.6 (4) | F6—P3—F1 | 91.3 (4) |
C28—C23—P1 | 117.9 (3) | F6—P3—F2 | 89.3 (5) |
C23—C24—H24 | 119.3 | F6—P3—F3 | 170.2 (6) |
C25—C24—C23 | 121.5 (4) | F6—P3—F4 | 93.3 (5) |
C25—C24—H24 | 119.3 | | |
| | | |
Cu1—P1—C11—C12 | 30.5 (4) | C18—C19—C20—C21 | −0.3 (8) |
Cu1—P1—C11—C16 | −151.3 (3) | C19—C20—C21—C22 | −0.2 (8) |
Cu1—P1—C17—C18 | 63.6 (3) | C20—C21—C22—C17 | 0.6 (7) |
Cu1—P1—C17—C22 | −118.3 (3) | C22—C17—C18—C19 | 0.0 (6) |
Cu1—P1—C23—C24 | −135.0 (3) | C23—P1—C11—C12 | −92.4 (3) |
Cu1—P1—C23—C28 | 41.2 (3) | C23—P1—C11—C16 | 85.8 (4) |
Cu1—P2—C34—C33 | −42.4 (3) | C23—P1—C17—C18 | −174.2 (3) |
Cu1—P2—C34—C35 | 132.5 (3) | C23—P1—C17—C22 | 3.9 (4) |
Cu1—P2—C38—C39 | −19.4 (4) | C23—C24—C25—C26 | −1.5 (7) |
Cu1—P2—C38—C43 | 160.4 (3) | C24—C23—C28—O2 | −176.2 (3) |
Cu1—P2—C44—C45 | −40.5 (3) | C24—C23—C28—C27 | 2.3 (6) |
Cu1—P2—C44—C49 | 141.6 (3) | C24—C25—C26—C27 | 1.8 (7) |
Cu1—O1—C2—C1 | −17.5 (4) | C25—C26—C27—C28 | −0.1 (6) |
Cu1—O1—C2—C3 | 164.1 (4) | C25—C26—C27—C29 | 175.9 (4) |
Cu1—N1—C1—C2 | 12.9 (5) | C26—C27—C28—O2 | 176.5 (3) |
Cu1—N1—C1—C6 | −165.7 (3) | C26—C27—C28—C23 | −2.0 (6) |
Cu1—N1—C9—C8 | 168.3 (4) | C26—C27—C29—C30 | 31.5 (6) |
Cu1—N1—C9—C10 | −9.6 (6) | C26—C27—C29—C31 | −88.2 (5) |
P1—C11—C12—C13 | 178.9 (3) | C26—C27—C29—C32 | 154.1 (4) |
P1—C11—C16—C15 | −179.2 (4) | C27—C29—C32—C33 | 31.7 (5) |
P1—C17—C18—C19 | 178.1 (3) | C27—C29—C32—C37 | −152.7 (4) |
P1—C17—C22—C21 | −178.5 (3) | C28—O2—C33—C32 | −29.2 (4) |
P1—C23—C24—C25 | 175.7 (3) | C28—O2—C33—C34 | 150.2 (3) |
P1—C23—C28—O2 | 7.3 (4) | C28—C23—C24—C25 | −0.5 (6) |
P1—C23—C28—C27 | −174.2 (3) | C28—C27—C29—C30 | −152.6 (4) |
P2—C34—C35—C36 | −172.8 (3) | C28—C27—C29—C31 | 87.7 (5) |
P2—C38—C39—C40 | −179.4 (4) | C28—C27—C29—C32 | −30.0 (5) |
P2—C38—C43—C42 | 179.2 (4) | C29—C27—C28—O2 | 0.3 (5) |
P2—C44—C45—C46 | −178.9 (4) | C29—C27—C28—C23 | −178.2 (4) |
P2—C44—C49—C48 | 177.8 (4) | C29—C32—C33—O2 | −3.8 (5) |
O1—C2—C3—C4 | 178.9 (5) | C29—C32—C33—C34 | 176.8 (4) |
O2—C33—C34—P2 | −6.8 (4) | C29—C32—C37—C36 | −174.1 (4) |
O2—C33—C34—C35 | 177.9 (3) | C30—C29—C32—C33 | 154.5 (4) |
N1—C1—C2—O1 | 4.7 (6) | C30—C29—C32—C37 | −29.9 (6) |
N1—C1—C2—C3 | −176.8 (4) | C31—C29—C32—C33 | −85.4 (5) |
N1—C1—C6—C5 | 175.9 (4) | C31—C29—C32—C37 | 90.2 (5) |
N1—C1—C6—C7 | −4.3 (7) | C32—C33—C34—P2 | 172.6 (3) |
C1—N1—C9—C8 | −0.7 (7) | C32—C33—C34—C35 | −2.7 (5) |
C1—N1—C9—C10 | −178.6 (4) | C33—O2—C28—C23 | −150.3 (3) |
C1—C2—C3—C4 | 0.7 (8) | C33—O2—C28—C27 | 31.2 (5) |
C1—C6—C7—C8 | 0.9 (8) | C33—C32—C37—C36 | 1.6 (6) |
C2—C1—C6—C5 | −2.7 (7) | C33—C34—C35—C36 | 2.2 (6) |
C2—C1—C6—C7 | 177.1 (4) | C34—P2—C38—C39 | 103.7 (3) |
C2—C3—C4—C5 | −2.3 (9) | C34—P2—C38—C43 | −76.4 (4) |
C3—C4—C5—C6 | 1.3 (9) | C34—P2—C44—C45 | −161.9 (3) |
C4—C5—C6—C1 | 1.2 (8) | C34—P2—C44—C49 | 20.2 (4) |
C4—C5—C6—C7 | −178.6 (6) | C34—C35—C36—C37 | 0.1 (6) |
C5—C6—C7—C8 | −179.3 (5) | C35—C36—C37—C32 | −2.1 (7) |
C6—C1—C2—O1 | −176.6 (4) | C37—C32—C33—O2 | −179.8 (3) |
C6—C1—C2—C3 | 1.8 (7) | C37—C32—C33—C34 | 0.8 (6) |
C6—C7—C8—C9 | 2.4 (9) | C38—P2—C34—C33 | −170.6 (3) |
C7—C8—C9—N1 | −2.6 (8) | C38—P2—C34—C35 | 4.3 (4) |
C7—C8—C9—C10 | 175.2 (6) | C38—P2—C44—C45 | 90.4 (3) |
C9—N1—C1—C2 | −177.1 (4) | C38—P2—C44—C49 | −87.5 (4) |
C9—N1—C1—C6 | 4.3 (6) | C38—C39—C40—C41 | −0.7 (7) |
C11—P1—C17—C18 | −67.9 (4) | C39—C38—C43—C42 | −1.0 (7) |
C11—P1—C17—C22 | 110.2 (4) | C39—C40—C41—C42 | 0.8 (8) |
C11—P1—C23—C24 | −6.4 (4) | C40—C41—C42—C43 | −1.1 (8) |
C11—P1—C23—C28 | 169.7 (3) | C41—C42—C43—C38 | 1.2 (8) |
C11—C12—C13—C14 | −0.1 (7) | C43—C38—C39—C40 | 0.7 (7) |
C12—C11—C16—C15 | −1.0 (7) | C44—P2—C34—C33 | 81.8 (3) |
C12—C13—C14—C15 | 0.0 (8) | C44—P2—C34—C35 | −103.4 (3) |
C13—C14—C15—C16 | −0.4 (8) | C44—P2—C38—C39 | −148.2 (3) |
C14—C15—C16—C11 | 1.0 (8) | C44—P2—C38—C43 | 31.6 (4) |
C16—C11—C12—C13 | 0.6 (6) | C44—C45—C46—C47 | 0.7 (7) |
C17—P1—C11—C12 | 159.7 (3) | C45—C44—C49—C48 | −0.1 (7) |
C17—P1—C11—C16 | −22.1 (4) | C45—C46—C47—C48 | 0.6 (8) |
C17—P1—C23—C24 | 99.5 (4) | C46—C47—C48—C49 | −1.6 (9) |
C17—P1—C23—C28 | −84.3 (3) | C47—C48—C49—C44 | 1.4 (8) |
C17—C18—C19—C20 | 0.4 (7) | C49—C44—C45—C46 | −0.9 (6) |
C18—C17—C22—C21 | −0.5 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···F1 | 0.85 | 2.08 | 2.802 (6) | 142 |
Some low-energy singlet electronic transitions for (I) calculated by TD–DFT topTransition | Energy (103 cm-1) | Wavelength (nm) | Oscillator strength | Major contributions |
T1 | 20.3 | 491.6 | 0 | H-3→LUMO(+45%) HOMO→LUMO (+44%) |
S1 | 25.9 | 386.0 | 0.0830 | HOMO→LUMO(+98%) |
S2 | 28.2 | 354.7 | 0.0048 | H-2→LUMO(+60%) H-1→LUMO(+32%) |
S3 | 29.3 | 340.9 | 0.0013 | H-1→LUMO(+68%) H-2→LUMO(29%) |
S4 | 31.2 | 320.3 | 0.0266 | H-3→LUMO(+93%) |
S5 | 31.2 | 320.2 | 0.0007 | H-6→LUMO(+47%) |
S6 | 31.9 | 313.3 | 0.0030 | HOMO→L+1(+95%) |
S7 | 33.3 | 300.1 | 0.0012 | HOMO→L+2(+75%) |
S8 | 33.7 | 296.4 | 0.0001 | H-5→LUMO(+50%) H-4→LUMO(36%) |
S9 | 33.8 | 295.9 | 0.0003 | H-6→LUMO(+65%) |
S10 | 34.5 | 290.2 | 0.0007 | H-4→LUMO(+41%) H-5→LUMO(+31%) H-6→LUMO(23%) |