Data on the characterization of (N-alkylsalicylaldiminato)bis(2-phenylpyridinato)iridium(III)

Abstract

Herein we report the synthesis, characterization data and photophysical properties of iridium(III) complexes having N-alkylated salicylaldimine and 2-phenylpyridine ligands. The structures of novel iridium complexes were assigned by ¹H and ¹³C NMR, ¹H–¹H COSY, NOESY, HMQC, HMBC, HRMS, IR and XRD analysis. For further information, we obtained photophysical properties in solution and crystalline states.

Specifications table

Subject area	Chemistry
More specific subject area	Metal complexes, Photoluminescence,
Type of data	Synthesis (text),1H NMR (Figures),13C NMR (Figures),1H–1H COSY (Figures), NOESY (Figures), HMQC (Figures), HMBC (Figures), IR (text), HRMS (text), m.p. (text), X-ray (Table and Figures), UV–vis (Figures and Table), emission (Figures and Table), emission lifetime (Table)
How data was acquired	1H NMR,13C NMR,1H–1H COSY, NOESY, HMQC, HMBC (Varian Unity–Inova 500 spectrometer) IR (Bruker Equinox 55 spectrometer) HRMS (Bruker micrOTOF II spectrometer) m.p. (Yanagimoto melting point apparatus) X-ray (Rigaku XtaLAB P100 diffractometer) UV–vis (Jasco V650 spectrometer) emission (Jasco FP-6500 spectrometer) emission lifetime (Optical Building Blocks Corp. EasyLife-X)
Data format	1H NMR (raw),13C NMR (raw),1H–1H COSY (raw), NOESY (raw), HMQC (raw), HMBC (raw), IR (raw), HRMS (raw), m.p. (raw), X-ray (analyzed), UV–Vis (raw), emission (raw), emission lifetime (analyzed)
Experimental factors	Synthesis, purification by SiO2chromatography and recrystallization
Experimental features	The characterization of the complexes was analyzed by1H NMR and13C NMR,1H–1H COSY, NOESY, HMQC, HMBC, FT-IR, APCI-MS, UV–vis and emission spectroscopies. The molecular structures and packings of the complexes in crystalline state were determined by XRD analysis.
Data source location	Toyonaka, Japan
Data accessibility	CCDC 1875572 (1a), CCDC 1875573 (1b) and CCDC 1875574 (1c) (http://www.ccdc.cam.ac.uk/conts/retrieving.html, email:deposit@ccdc.cam.ac.uk.).
Related research article	S. Sprouse, K. A. King, P. J. Spellane, and R. J. Watts, Photophysical effects of metal-carbon σ bonds in ortho-metalated complexes of iridium(III) and rhodium(III), J. Am. Chem. Soc. 106 (1984) 6647–6653.

Value of the data •Data of 1H NMR, 13C NMR, 1H–1H COSY, NOESY, HMQC and HMBC were given for characterization and to check purity of synthesized iridium complexes, which provide valuable resource for various research area. •Data of XRD analysis were provided for the structure of complexes and intermolecular interactions in crystalline state, which are useful information on the solid-state emission. •Photophysical data of UV–vis, emission and emission lifetime were provided for useful information on the development of phosphorescent materials.

1. Data

In this article we share the synthesis and characterization of iridium complexes 1a–1d that exhibit phosphorescence in the solution and crystalline states. Fig. 1, Fig. 2 demonstrate ¹H and ¹³C NMR spectra of 1a–1d in CDCl₃. Assignment of ¹H NMR signals was made by ¹H–¹H COSY and NOESY experiments as shown in Fig. 3, Fig. 4. Assignment of ¹³C NMR was made by HMQC and HMBC experiments as shown in Fig. 5 and Fig. 6. Fig. 7, Fig. 8 show ORTEP drawings and packing of 1a–1c determined by XRD analysis. Table 1 shows crystallographic data for 1a–1c. Fig. 9, Fig. 10 show UV–vis spectra for 1a–1d in 2-MeTHF and solid state. Fig. 11, Fig. 12 show emission spectra in 2-MeTHF and crystalline state. Table 2 shows photophysical data of 1a–1c in 2-MeTHF and crystalline state.

Fig. 1.

¹H NMR spectra (500 MHz) of complexes (a, e) 1a, (b, f) 1b, (c, g) 1c and (d, h) 1d. (a–d) Aromatic and (e–h) aliphatic regions.

Fig. 2.

¹³C NMR spectra (125 MHz) of complexes (a, e) 1a, (b, f) 1b, (c, g) 1c and (d, h) 1d. (a–d) Aromatic and (e–h) aliphatic regions.

Fig. 3.

¹H–¹H COSY spectra (500 MHz) of complexes (a, b) 1a, (c, d) 1b, (e, f) 1c and (g, h) 1d in CDCl₃ (298 K, number of t₁ increments = 1024, number of t₂ increments = 1024, number of scans = 16). (a, c, e, g) Aromatic and (b, d, f, h) aliphatic regions.

Fig. 4.

NOESY spectra (500 MHz) of complexes (a) 1a, (b) 1b, (c) 1c and (d) 1d in CDCl₃ (298 K, mixing time = 1.00 s, number of t₁ increments = 1024, number of t₂ increments = 1024, number of scans = 64).

Fig. 5.

HMQC spectra (500 MHz) of complexes (a) 1a, (b) 1b, (c) 1c and (d) 1d in CDCl₃ (298 K, number of t₁ increments = 1024, number of t₂ increments = 1024).

Fig. 6.

HMBC spectra (500 MHz) of complexes (a) 1a, (b) 1b, (c) 1c and (d) 1d in CDCl₃ (298 K, number of t₁ increments = 1024, number of t₂ increments = 1024).

Fig. 7.

ORTEP representations of (a) Δ-1a, (b) Δ- 1b and (c) Δ-1c as their racemic crystals. Thermal ellipsoids are shown at the 50% probability level.

Fig. 8.

Packing in (a) 1a, (b) 1b and (c) 1c crystals.

Table 1.

Crystallographic data for 1a–1c.

	1a	1b	1c
formula	C34H32N3OIr	C37H38NO3Ir	C43H50N3OIr
Mr	690.87	732.95	817.11
T/K	113	113	113
crystal color, habit	yellow, chip	yellow, chip	yellow, chip
crystal size/mm	1.00 × 0.50 × 0.1	0.20 × 0.20 × 0.05	0.20 × 0.05 × 0.01
crystal system	monoclinic	monoclinic	triclinic
space group	P21/c (#14)	P21/n (#14)	P-1 (#2)
a/Å	16.290(2)	16.334 (2)	9.6352(16)
b/Å	7.9.8165(11)	9.8695(13)	15.051(2)
c/Å	17.405(2)	19.189(3)	26.536(4)
α/°	90	90	75.107(5)
β/°	97.790(3)	94.793(4)	89.320(7)
γ/°	90	90	87.117(7)
V/Å3	2757.6(6)	3082.7(7)	3714.3(10)
Z	4	4	4
ρcalcd/g·cm−3	1.664	1.579	1.461
μ (MoKα)/cm−1	48.877	43.772	36.411
F(000)	1368.00	1464.00	1656.00
2θmax/°	55.0	55.0	55.0
No. of reflns measd	28631	35714	71214
No. of obsd reflns	6304	7043	16964
No. variables	352	379	865
R1 (I > 2σ(I))a	0.0378	0.0291	0.0485
wR2 (all reflns)b	0.912	0.0696	0.1166
Goodness of fit	0.975	1.008	0.9971

^aR₁ = Σ(|F_o|–|F_c|)/Σ(|F_o|).

^bwR₂ = [Σ[w(F_o²–F_c²)²]/Σw(F_o²)²]^1/2.

Fig. 9.

UV–vis spectra of complexes 1a–1d in 2-MeTHF (2.0 × 10⁻⁴ M) at 298 K.

Fig. 10.

Normalized diffuse reflectance UV–vis spectra of crystals 1a–1d at 298 K.

Fig. 11.

Emission spectra of complexes 1a–1d in 2-MeTHF (2.0 × 10⁻⁴ M) at 77 K (λ_ex = 415 nm).

Fig. 12.

Normalized emission spectra of crystals 1a–1d at (a) 298 K and (b) 77 K (λ_ex = 450 nm).

Table 2.

Photophysical data for 1a–1d^[a].

Complex	State	λabs [nm]	λem [nm][c]	Φ[c,d]	τ [μs][e]	kr × 10−5 [s−1][f]	knr × 10−5 [s−1][f]
1a	2-MeTHF[b]	397	–[g] (561)	–[g] (0.13)	(5.03)	(0.26)	(2.0)
1b	2-MeTHF[b]	397	–[g] (527, 564)	–[g] (0.13)	(4.98)	(0.26)	(2.0)
1c	2-MeTHF[b]	397	–[g] (572)	–[g] (0.15)	(5.09)	(0.29)	(2.0)
1d	2-MeTHF[b]	397	–[g] (538, 568)	–[g] (0.14)	(4.87)	(0.29)	(2.1)
1a	crystal	399	576 (550, 584)	0.02 (0.06)	(0.61)	(0.33)	(16)
1b	crystal	399	573 (541, 578)	0.03 (0.12)	(0.47)	(0.64)	(21)
1c	crystal	399	579 (553, 580)	0.02 (0.11)	(0.30)	(0.67)	(33)
1d	crystal	399	574 (541, 572)	0.03 (0.10)	(0.51)	(0.59)	(19)

^[a] Data were obtained at 298 K and 77 K. Values in parentheses are those measured at 77 K.

^[b] 2.0 × 10⁻⁴ M.

^[c] λ_ex = 415 nm.

^[d] Determined by the absolute method using an integrating sphere.

^[e] λ_ex = 415 nm.

^[f] Determined based on the quantum yield and lifetime.

^[g] No data due to non-emission properties at 298 K.

2. Experimental design, materials, and methods

Melting points were measured in a glass capillary using a Yanagimoto melting point apparatus. ¹H NMR, ¹³C NMR, ¹H–¹H COSY, NOESY, HMQC and HMBC spectra of samples in a deuterated chloroform were recorded on a Varian Unity–Inova 500 spectrometer. ¹H NMR and ¹³C NMR spectra were referenced to a peak of an internal TMS (0.0 ppm for ¹H) and a deuterated chloroform (77.0 ppm for ¹³C), respectively. IR spectra was recorded on a Bruker Equinox 55 spectrometer in KBr disk at room temperature. HRMS was obtained by using a Bruker micrOTOF II spectrometer. UV–vis and emission spectra in 2-MeTHF were recorded on a Jasco V650 and a Jasco FP-6500 spectrometer respectively. Emission lifetime in 2-MeTHF was measured on an Optical Building Blocks Corp. EasyLife-X.

Crystals of 1a–1c suitable for X-ray diffraction studies were prepared by recrystallization from hexane/ethyl acetate mixture, and analyzed using a Rigaku XtaLAB P200 diffractometer with Mo-Kα radiation. The structures of 1a–1c were solved by direct methods and refined using the full-matrix least-squares method. In subsequent refinements, the function Σω(F²_o–F²_c)² was minimized, where F_o and F_c are the observed and calculated structure factor amplitudes, respectively. The positions of non-hydrogen atoms were determined from difference Fourier electron-density maps and refined anisotropically. All calculations were performed with the Crystal Structure crystallographic software package, and illustrations were drawn using ORTEP [1].

3. Synthesis

Complexes 1a–1d were prepared by reaction of μ-chlorobis(2-phenylpyridine)iridium dimer [2] with the corresponding salicylaldimine and Na₂CO₃ in boiling 2-ethoxyethanol.

3.1. Complex 1a (n = 5)

M.p. = 272–273 °C, IR (KBr): 3050, 2950, 2922, 2852, 1616, 1582, 1530, 1475, 1452, 1417, 1356, 1156, 910, 755 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) δ 0.57–0.73 (m, 5 H, H^16,18), 0.83–0.97 (m, 3 H, H^15,17), 1.08–1.17 (m, 1 H, H¹⁵), 3.10 (ddd, J = 5.5, 10.5, 10.5 Hz, 1 H, H¹⁴), 3.33 (ddd, J = 5.5, 10.5, 10.5 Hz, 1 H, H¹⁴), 6.13 (dd, J = 1.1, 7.5 Hz, 1 H, H^8’), 6.36 (dd, J = 1.1, 7.5 Hz, 2 H, H⁸), 6.36 (ddd, J = 1.4, 6.9, 7.8 Hz, 1 H, H¹¹), 6.66 (dd, J = 1.4, 8.8 Hz, 1 H, H⁹), 6.66 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H⁷), 6.72 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H^7’), 6.80 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H⁶), 6.82 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H^6’), 6.96 (ddd, J = 1.3, 5.7, 7.3 Hz, 1 H, H^2’), 7.06 (dd, J = 1.8, 7.8 Hz, 1 H, H¹²), 7.10 (ddd, J = 1.2, 5.7, 7.3 Hz, 1 H, H²), 7.17 (ddd, J = 1.8, 6.9, 8.8 Hz, 1 H, H¹⁰), 7.53 (dd, J = 1.4, 7.8 Hz, 1 H, H^5’), 7.57 (dd, J = 1.4, 7.8 Hz, 1 H, H⁵), 7.65 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H^3’), 7.73 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H³), 7.82 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H^4’), 7.87 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H⁴), 8.01 (s, 1 H, H¹³), 8.43 (ddd, J = 0.7, 1.5, 5.7 Hz, 1 H, H^1’), 8.86 (ddd, J = 0.7, 1.5, 5.7 Hz, 1H, H¹); ¹³C NMR (125 MHz, CDCl₃) δ 13.9 (C¹⁸), 22.1 (C¹⁷), 28.8 (C¹⁶), 30.5 (C¹⁵), 64.3 (C¹⁴), 112.9 (C¹¹), 118.1 (C^4’), 118.8 (C⁴), 120.1 (C⁶), 121.1 (C^6’), 121.2 (C^12a), 121.4 (C^2’), 121.6 (C²), 123.7 (C^5’), 123.9 (C⁵), 124.0 (C⁹), 129.25 (C^{7 or 7’}), 129.28 (C^{7 or 7’}), 131.8 (C^8’), 133.38 (C¹⁰), 133.41 (C⁸), 134.7 (C¹²), 136.5 (C^3’), 136.7 (C³), 144.49 (C^{5 or 5’}), 144.50 (C^{5 or 5’}), 148.77 (C^{1 or 1’}), 148.83 (C^{1 or 1’}), 150.2 (C^8a), 153.2 (C^8a’), 161.6 (C¹³), 166.0 (C^9a), 168.5 (C^4a), 169.0 (C^4a’); HRMS (APCI): m/z calcd for ¹⁹¹IrC₃₄H₃₂N₃O: 689.2146; found: 689.2147 [M⁺].

3.2. Complex 1b (n = 8)

M.p. = 239–240 °C, IR (KBr): 3029, 2919, 2851, 1617, 1582, 1475, 1453, 1359, 1157, 1059, 1030, 758 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) δ 0.57–0.75 (m, 2 H, H¹⁶), 0.78–0.93 (m, 6 H, H^15a,17,21), 1.01 (dddd, J = 7.5, 7.5, 7.5, 7.5 Hz, 2 H, H¹⁸), 1.08–1.14 (m, 3 H, H^15b,19), 1.22 (dddd, J = 7.5, 7.5, 7.5, 7.5 Hz, 2 H, H²⁰), 3.09 (ddd, J = 5.8, 10.1, 10.1 Hz, 1 H, H¹⁴), 3.33 (ddd, J = 5.8, 10.1, 10.1 Hz, 1 H, H¹⁴), 6.13 (dd, J = 1.1, 7.5 Hz, 1 H, H^8’), 6.36 (dd, J = 1.1, 7.5 Hz, 1 H, H⁸), 6.36 (ddd, J = 1.4, 6.9, 7.8 Hz, 1 H, H¹¹), 6.66 (dd, J = 1.4, 8.8 Hz, 1 H, H⁹), 6.66 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H⁷), 6.72 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H^7’), 6.80 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H⁶), 6.82 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H^6’), 6.96 (ddd, J = 1.3, 5.7, 7.3 Hz, 1 H, H^2’), 7.06 (dd, J = 1.8, 7.8 Hz, 1 H, H¹²), 7.10 (ddd, J = 1.2, 5.7, 7.3 Hz, 1 H, H²), 7.17 (ddd, J = 1.8, 6.9, 8.8 Hz, 1 H, H¹⁰), 7.53 (dd, J = 1.4, 7.8 Hz, 1 H, H^5’), 7.56 (dd, J = 1.4, 7.8 Hz, 1 H, H⁵), 7.65 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H^3’), 7.73 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H³), 7.82 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H^4’), 7.87 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H⁴), 8.01 (s, 1 H, H¹³), 8.42 (ddd, J = 0.7, 1.5, 5.7 Hz, 1 H, H^1’), 8.86 (ddd, J = 0.7, 1.5, 5.7 Hz, 1H, H¹); ¹³C NMR (125 MHz, CDCl₃) δ 14.1 (C²¹), 22.6 (C²⁰), 26.7 (C¹⁶), 29.0 (C^{17 or 18}), 29.1 (C^{17 or 18}), 30.9 (C¹⁵), 31.7 (C¹⁹), 64.3 (C¹⁴), 112.8 (C¹¹), 118.0 (C^{4 or 4’}), 118.1 (C^{4 or 4’}), 120.08 (C⁶), 121.14 (C^6’), 121.17 (C^12a), 121.4 (C^2’), 121.6 (C²), 123.7 (C^5’), 123.9 (C⁵), 124.1 (C⁹), 129.2 (C^{7 or 7’}), 129.3 (C^{7 or 7’}), 131.8 (C^8’), 133.3 (C¹⁰), 133.5 (C⁸), 134.7 (C¹²), 136.4 (C^3’), 136.7 (C³), 144.46 (C^{5 or 5’}), 144.49 (C^{5 or 5’}), 148.75 (C^{1 or 1’}), 148.81 (C^{1 or 1’}), 150.3 (C^8a), 153.2 (C^8a’), 161.6 (C¹³), 165.8 (C^9a), 168.5 (C^4a), 169.0 (C^4a’); HRMS (APCI): m/z calcd for ¹⁹¹IrC₃₇H₃₈N₃O: 731.2615; found: 787.2611 [M⁺].

3.3. Complex 1c (n = 14)

M.p. = 187.5–188.5 °C, IR (KBr): 3041, 2922, 2851, 2356, 1617, 1475, 1454, 1059. 756, 734, 675 cm⁻¹; ¹H NMR (500 MHz,CDCl₃) δ 0.58–0.76 (m, 2 H, H¹⁶), 0.78–0.93 (m, 6 H, H^15a,17,27), 1.01 (dddd, J = 7.5, 7.5, 7.5, 7.5 Hz, 2 H, H¹⁸), 1.09–1.16 (m, 3 H, H^15b,19), 1.16–1.33 (m, 14 H, H²⁰⁻²⁶), 3.10 (ddd, J = 5.8, 10.1, 10.1 Hz, 1 H, H¹⁴), 3.34 (ddd, J = 5.8, 10.1, 10.1 Hz, 1 H, H¹⁴), 6.14 (dd, J = 1.1, 7.5 Hz, 1 H, H^8’), 6.37 (dd, J = 1.1, 7.5 Hz, 1 H, H⁸), 6.38 (ddd, J = 1.4, 6.9, 7.8 Hz, 1 H, H¹¹), 6.67 (dd, J = 1.4, 8.8 Hz, 1 H, H⁹), 6.67 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H⁷), 6.73 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H^7’), 6.81 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H⁶), 6.81 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H^6’), 6.98 (ddd, J = 1.3, 5.7, 7.3 Hz, 1 H, H^2’), 7.07 (dd, J = 1.8, 7.8 Hz, 1 H, H¹²), 7.11 (ddd, J = 1.2, 5.7, 7.3 Hz, 1 H, H²), 7.18 (ddd, J = 1.8, 6.9, 8.8 Hz, 1 H, H¹⁰), 7.55 (dd, J = 1.4, 7.8 Hz, 1 H, H^5’), 7.57 (dd, J = 1.4, 7.8 Hz, 1 H, H⁵), 7.66 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H^3’), 7.74 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H³), 7.83 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H^4’), 7.88 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H⁴), 8.02 (s, 1 H, H¹³), 8.43 (ddd, J = 0.7, 1.5, 5.7 Hz, 1 H, H^1’), 8.87 (ddd, J = 0.7, 1.5, 5.7 Hz, 1H, H¹); ¹³C NMR (125 MHz, CDCl₃) δ 14.1 (C²⁷), 22.7 (C²⁶), 26.7 (C¹⁶), 29.1 (C¹⁷), 29.35, 29.42, 29.5, 29.6, 29.66, 29.71, 30.9 (C¹⁵), 31.9 (C²⁵), 64.3 (C¹⁴), 112.9 (C¹¹), 118.0 (C^4’), 118.8 (C⁴), 120.2 (C⁶), 121.12 (C^6’), 121.14 (C^12a), 121.4 (C^2’), 121.6 (C²), 123.7 (C^5’), 123.95 (C⁵), 123.99 (C⁹), 129.2 (C^{7 or 7’}), 129.3 (C^{7 or 7’}), 131.8 (C^8’), 133.39(C¹⁰), 133.41 (C⁸), 134.7 (C¹²), 136.5 (C^3’), 136.6 (C³), 144.46 (C^{5 or 5’}), 144.50 (C^{5 or 5’}), 148.8 (C^{1 or 1’}), 148.9 (C^{1 or 1’}), 150.2 (C^8a), 153.3 (C^8a’), 161.6 (C¹³), 165.7 (C^9a), 168.5 (C^4a), 169.0 (C^4a’); HRMS (APCI): m/z calcd for ¹⁹¹IrC₄₃H₅₀N₃O: 815.3554; found: 815.3545 [M⁺].

3.4. Complex 1d (n = 18)

M.p. = 176–177 °C, IR (KBr): 3048, 2923, 2851, 1617, 1583, 1532, 1475, 1453, 1416, 1357, 1332, 1157 cm⁻¹; ¹H NMR (500 MHz, CDCl₃) δ 0.58–0.75 (m, 2 H, H¹⁶), 0.79–0.93 (m, 6 H, H^15a,17,31), 1.01 (dddd, J = 7.5, 7.5, 7.5, 7.5 Hz, 2 H, H¹⁸), 1.08–1.15 (m, 3 H, H^15b,19), 1.15–1.33 (m, 22 H, H²⁰⁻³⁰), 3.10 (ddd, J = 5.8, 10.1, 10.1 Hz, 1 H, H¹⁴), 3.34 (ddd, J = 5.8, 10.1, 10.1 Hz, 1 H, H¹⁴), 6.14 (dd, J = 1.1, 7.5 Hz, 1 H, H^8’), 6.37 (dd, J = 1.1, 7.5 Hz, 1 H, H⁸), 6.38 (ddd, J = 1.4, 6.9, 7.8 Hz, 1 H, H¹¹), 6.67 (dd, J = 1.4, 8.8 Hz, 1 H, H⁹), 6.67 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H⁷), 6.73 (ddd, J = 1.4, 7.5, 7.5 Hz, 1 H, H^7’), 6.81 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H⁶), 6.81 (ddd, J = 1.1, 7.5, 7.8 Hz, 1 H, H^6’), 6.98 (ddd, J = 1.3, 5.7, 7.3 Hz, 1 H, H^2’), 7.07 (dd, J = 1.8, 7.8 Hz, 1 H, H¹²), 7.11 (ddd, J = 1.2, 5.7, 7.3 Hz, 1 H, H²), 7.18 (ddd, J = 1.8, 6.9, 8.8 Hz, 1 H, H¹⁰), 7.55 (dd, J = 1.4, 7.8 Hz, 1 H, H^5’), 7.57 (dd, J = 1.4, 7.8 Hz, 1 H, H⁵), 7.66 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H^3’), 7.74 (ddd, J = 1.5, 7.3, 8.0 Hz, 1 H, H³), 7.83 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H^4’), 7.88 (ddd, J = 0.7, 1.2, 8.0 Hz, 1 H, H⁴), 8.02 (s, 1 H, H¹³), 8.43 (ddd, J = 0.7, 1.5, 5.7 Hz, 1 H, H^1’), 8.87 (ddd, J = 0.7, 1.5, 5.7 Hz, 1H, H¹); ¹³C NMR (125 MHz, CDCl₃) δ 14.1 (C³¹), 22.7 (C³⁰), 26.7 (C¹⁶), 29.0 (C¹⁷), 29.35, 29.42, 29.5, 29.61, 29.65, 29.67, 29.71, 30.9 (C¹⁵), 31.9 (C²⁹), 64.3 (C¹⁴), 112.8 (C¹¹), 118.0 (C^4’), 118.8 (C⁴), 120.2 (C⁶), 121.1 (C^6’), 121.2 (C^12a), 121.4 (C^2’), 121.6 (C²), 123.7 (C^5’), 123.9 (C⁵), 124.1 (C⁹), 129.25 (C^{7 or 7’}), 129.27 (C^{7 or 7’}), 131.8 (C^8’), 133.3 (C¹⁰), 133.4 (C⁸), 134.7 (C¹²), 136.4 (C^3’), 136.6 (C³), 144.46 (C^{5 or 5’}), 144.49 (C^{5 or 5’}), 148.76 (C^{1 or 1’}), 148.83 (C^{1 or 1’}), 150.3 (C^8a), 153.2 (C^8a’), 161.6 (C¹³), 166.0 (C^9a), 168.5 (C^4a), 169.0 (C^4a’); HRMS (APCI): m/z calcd for ¹⁹¹IrC₄₇H₅₈N₃O: 871.4180; found: 871.4174 [M⁺]. Anal. Calcd for IrC₄₇H₅₈N₃O: C, 64.65; H, 6.70; N, 4.81. Found: C, 64.46, H, 6.61, N, 4.76.

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.