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. 2024 Mar 27;4(4):1623–1631. doi: 10.1021/jacsau.4c00105

Extended Quinolizinium-Fused Corannulene Derivatives: Synthesis and Properties

Lin Huang †,‡,§, Qing Wang ∥,⊥, Peng Fu †,‡,§, Yuzhu Sun †,‡,§, Jun Xu ∥, Duncan L Browne #, Jianhui Huang †,‡,§,*
PMCID: PMC11040561  PMID: 38665663

Abstract

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Reported here is the design and synthesis of a novel class of extended quinolizinium-fused corannulene derivatives with curved geometry. These intriguing molecules were synthesized through a rationally designed synthetic strategy, utilizing double Skraup–Doebner–Von Miller quinoline synthesis and a rhodium-catalyzed C–H activation/annulation (CHAA) as the key steps. Single-crystal X-ray analysis revealed a bowl depth of 1.28–1.50 Å and a unique “windmill-like” shape packing of 12a(2PF6–) due to the curvature and incorporation of two aminium ions. All of the newly reported curved salts exhibit green to orange fluorescence with enhanced quantum yields (Φf = 9–13%) and improved dispersibility compared to the pristine corannulene (Φf = 1%). The reduced optical energy gap and lower energy frontier orbital found by doping extended corannulene systems with nitrogen cations was investigated by UV–vis, fluorescence, and theoretical calculations. Electrochemical measurements reveal a greater electron-accepting behavior compared with that of their pyridine analogues. The successful synthesis, isolation, and evaluation of these curved salts provide a fresh perspective and opportunity for the design of cationic nitrogen-doped curved aromatic hydrocarbon-based materials.

Keywords: nitrogen doped PAHs, corannulene, nitrogen cations, intermolecular packing, photophysical properties

Introduction

Curved polycyclic aromatic hydrocarbons (PAHs) have attracted significant attention due to their unique properties.1−10 Corannulene, with a C5v symmetric and partial fullerene-like structure, is a typical bowl-shaped polycyclic aromatic arene.11,12 It has unique properties originating from its distorted structure, such as intermolecular packing,13−15 dynamic inversion behaviors,16−20 and electron deficiency21−23 compared with that of classical planar graphene forms. Corannulene derivatives have also been widely applied in research fields such as polymer,24 organic field effect transistors (OFETs),25−27 sensors,28,29 solar cells,30,31 host–guest chemistry,32−34 and organic light emitters.35,36 Doping of heteroatoms into polycyclic aromatic systems is of significant interest, as such heteroatoms can perturb the electronic structures of the original carbon-based compounds and thus offer possibilities for new applications.37−43 Nonetheless, only limited examples of heteroatom-doped curved systems have been reported, which is in large part hindered by the synthetic challenges of such systems. The most commonly found examples are those with nitrogen atoms at the peripheral positions or within the polycyclic skeleton (Figure 1).44−52

Figure 1.

Figure 1

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(a) Previous reports on pyrrolic and pyridinic nitrogen-incorporated corannulenes within the polycyclic skeleton (1a, 1b, and 2) and at the peripheral positions (3). (b) Diazapentabenzocorannulenium 4. (c) Extended quinolizinium-fused corannulenes.

The inclusion of pyridinic, pyrrolic, or cationic nitrogen atoms represents a crucial strategy in tuning and inducing distinct electronic effects.39 Several examples have been synthesized, such as extended π-conjugated azacorannulenes (1a, 1b) bearing a pyrrolic-type nitrogen at the hub position of corannulene core by Shinokubo et al. and Nozaki et al.,44,45 pyridine-embedded corannulene 2, with a nitrogen atom at the rim position, by Scott et al.,46 and peripherally nitrogen-incorporated azaindenocorannulene 3 by Siegel et al.47 (Figure 1a). Cationic nitrogen-incorporated analogues have been less explored, mainly due to the reactivity and synthetic challenge. Only recently, a cationic corannulene bearing a central imidazolium core was reported by Ito et al. (Figure 1b), showing high water dispersibility and biocompatibility, despite a lack of hydrophilic substituents.48 Planar cationic nitrogen-doped PAHs have shown interesting photoelectric and self-assembly properties.53−57 We envisioned that the introduction of curvature may, in combination with cationic nitrogen doping, afford modified optoelectronic properties. Dynamic bowl inversion behavior also provides the possibility of atropisomeric chirality and column-like packing structures.58 Moreover, the disrupted π-electron delocalization and π–π interactions of all carbon curved systems will be enhanced by the nitrogen cation doping, which induces a lower band gap and higher electron affinity.59,60 Herein, we designed and synthesized a novel class of extended corannulene derivatives bearing one (11a and 11b) or two cationic nitrogen atoms (12a and 12b) at the peripheral positions, achieved by a rationally designed synthetic strategy, which includes a double Skraup–Doebner–Von Miller pyridine synthesis and a rhodium-catalyzed C–H activation/annulation (CHAA) reaction as key steps. It was anticipated that these curved π-extended cationic nitrogen-containing PAHs may exhibit interesting structure, properties, and function, compared to their planar analogues.

Results and Discussion

Design and Synthesis

Our synthetic strategy to extended quinolizinium-fused corannulenes 11a–12b centered on access to the key intermediate diaminocorannulene 9, via the regioselective bromination of corannulene 8. From intermediate 9, the bilateral construction of pyridine through a double Skraup–Doebner–Von Miller synthesis was envisioned as a prequel to a final transition-metal-catalyzed CHAA process to furnish the cationic quinoline moiety.61,62 Halocorannulenes have been proven particularly important for the introduction of an amino group through a Pd-catalyzed amination reaction. While some of them, like bromocorannulene, pentachlorocorannulene, and decachlorocorannulene, have been synthesized,63 dihalogenated-corannulenes have not been extensively studied because of the challenges in controlling the selectivity of halogenation. As illustrated in Scheme 1, to obtain the critical intermediate 4,9-dibromocorannulene 8, we commenced by adopting the ring-closure method reported by Rabideau and Sygula,64 Siegel et al.,65 and Cao et al.27 using diphenylacetylene as dienophile. Diels–Alder cycloaddition between carbinol 5 and diphenylacetylene in acetic anhydride at 150 °C led to the formation of bisphenyl-substituted tetramethylfluoranthene 6 in a 42% yield after the elimination of a CO molecule. Treatment of 6 with 6 equiv of N-bromosuccinimide (NBS) under sun lamp irradiation exclusively produced hexabromo-fluoranthene 7, likely owing to a level of steric control imparted by the phenyl groups. Notably, the use of excess NBS or reaction time can overcome this steric control and lead to overbromination. 4,9-Dibromo-1,2-diphenylcorannulene 8 can be furnished in an 80% yield by heating hexabromo-fluoranthene 7 with sodium hydroxide in dioxane/water (∼3:1) to reflux for 16 h.

Scheme 1. Synthetic Route to the Extended Quinolizinium-Fused Corannulenes 11a–12b.

Scheme 1

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Efficient and rapid access to π-extended fused heteroaromatics is of great importance in materials science.40,43,66,67 The synthesis of the crucial second intermediate, dipyridocorannulene 10, from dibromocorannulene 8 was not straightforward. Diaminocorannulene 9 was synthesized first through a Buchwald–Hartwig amination using benzophenone imine, followed by hydrolysis.50,68 Subsequently, a double Skraup–Doebner–Von Miller quinoline synthesis,69 employing acrolein diethylacetal as the reactant in 1 M HCl, was utilized for the preparation of dipyridocorannulene 10 from 9. Recently, the direct functionalization of C–H bonds in organic compounds has emerged as a potent and optimal approach for generating both carbon–carbon and carbon–heteroatom bonds.70−72 Based on our continuous research interests in transition-metal-catalyzed CHAA reactions,73−75 we have attempted the use of palladium, ruthenium, and rhodium catalysts for the final ring closure. The use of both palladium and ruthenium catalysts failed to provide any of the desired product. However, rhodium catalyst76 Cp*RhCl2 afforded the target extended quinolizinium-fused corannulenes successfully. Silver triflate was chosen as the oxidant in this transition, for its efficacy in facilitating the annulation process. This method led to the synthesis of both monoquinolizinium extended corannulenes 11a–b (30–53%) and bis-quinolizinium extended corannulenes 12a–b (39–42%) in good yields. Notably, this is the first successful application of a transition-metal-catalyzed CHAA reaction in such a corannulene-based curved π-conjugated system.

X-ray Crystallography

Due to unsuccessful attempts to obtain single crystals of 12a suitable for X-ray diffraction, an anion metathesis reaction of a solution of 12a (in acetonitrile) was attempted with potassium hexafluorophosphate (KPF6) in water to obtain the corresponding hexafluorophosphate salt 12a(2PF6–). Single crystals of 12a(2PF6–) were obtained by the slow evaporation of a toluene/methanol solution at room temperature, which crystallized in the P2/c space group (Figure 2). The bowl depth, defined as the perpendicular distance from the center of the hub (C1–C5 ring) to the parallel planes containing the carbon atoms C20–C22 and C25–C27 is in the range of 1.28–1.50 Å (Figure 2B). This bowl depth is larger than that of corannulene (0.87 Å),77 and the curvature of 12a(2PF6–) is further evaluated by Haddon’s π-orbital axis vector (POAV)78,79 angles. As shown in Figure 2A, the POAV angles around the central five-membered ring are in the range of 7.7–8.2°, which are similar to that of corannulene (8.3°).80 These findings suggest that 12a(2PF6–) has a curvature akin to that of corannulene, yet it exhibits greater depth due to its π-extended architecture. Furthermore, compound 12b, bearing both n-butyl and phenyl substituents, exhibits five distinct split peaks corresponding to the phenyl protons in its 1H NMR spectrum (Figure S32). This phenomenon was not observed in dipyridocorannulene 10, which has two adjacent phenyl groups and fused pyridine rings (Figure S24). This nonsymmetric feature evidences that the bowl-to-bowl inversion in 12b occurs slower than the NMR timescale at room temperature, indicating a higher inversion energy barrier and a deeper bowl depth, aligning with Siegel’s reported correlation between bowl depth and inversion barrier.20 The inversion barrier was further studied by density functional theory (DFT) calculation at the B3LYP/6-311G (2d, p) level of theory to be 14.0 kcal mol–1, as displayed in Figure 3. This value is larger than that of pristine corannulene (theoretical value: 10.7–11.0 kcal mol–1).20,81

Figure 2.

Figure 2

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OPTER structure of 12a(2PF6–) with thermal ellipsoids at 45% probability. (A) Top view including POAV angles of C1–C5 (hydrogen atoms and PF6– are omitted for clarity). (B) Side view including the calculated bowl depth (hydrogen atoms and phenyl groups have been omitted for clarity).

Figure 3.

Figure 3

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Energy diagram of bowl inversion for 12a(2PF6–) through a planar transition intermediate TS (PF6– counterions and phenyl groups are omitted for clarity).

The aromaticity of 12a(2PF6–) was evaluated by nucleus-independent chemical shift (NICS) calculations and anisotropy of the induced current density (ACID) analyses at the B3LYP/6-311G (2d, p) level of theory (Figure 4A, B). A positive NICS (0) value of 11.4 (Figure 4A) and an anticlockwise paratropic ring current (Figure 4B) were predicted for the pentagon (ring A), indicating a localized antiaromaticity of the five-membered ring, which was consistent to that observed for the pristine corannulene. Meanwhile, the NICS (0) of peripheral rings were calculated to be −4.7 (ring B), −2.7 (ring C), and −8.4 (ring D), respectively, suggesting their aromaticity. Interestingly, the NICS (0) values of ring E and ring F, sharing a nitrogen cation dopant, were 0.1 and −8.9, respectively. The opposite values indicated their weak antiaromaticity and aromaticity, respectively. The ACID plot disclosed a distinct clockwise diatropic ring current along the periphery of the whole π-conjugated framework (Figures 4B and S11), indicating a global aromaticity crossed over two quinolizinium motifs.

Figure 4.

Figure 4

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Aromaticity and packing structure of 12a(2PF6–) (ball and stick). (A) NICS (0) values. (B) ACID plot of 12a(2PF6–) (phenyl groups are omitted) by using the AICD 2.0 software. The magnetic field is perpendicular to the molecular plane and points out of the image. The clockwise/anticlockwise circles labeled with red/dark blue arrows indicate the diatropic/paratropic ring current, respectively. (C) Side view of a “windmill-like” unit. Distance between two cationic nitrogen atoms is depicted in deep blue, and solvent molecules (toluene) are omitted for clarity. (D) Packing along the b-axis, a blue windmill is superimposed; solvent molecules (toluene) are depicted in purple, and two types of vacant space are depicted in blue and red, respectively.

Interestingly, in these infinite stacks, a distinctive “windmill-like” repeating unit is formed by four 12a(2PF6–) molecules, while the hexafluorophosphate counterions and nitrogen cations align in a linear fashion (Figure 4C,D). In a “windmill-like” unit, four molecules show a concave/concave (cc/cc) packing mode, while between the “windmill-like” units, they are arranged in a convex/convex (cv/cv) manner. This results in the formation of two main types of vacant space within the “windmill-like” and between the “windmill-like” units, depicted in blue and red, respectively (Figure 4D). The distance of the blue space containing hexafluorophosphate is 7.33 Å, and the rectangular red space containing both hexafluorophosphate and solvent toluene molecules has dimensions of 14.4 Å (length) and 4.75 Å (width). The curvature of 12a(2PF6–) leads to unique cc/cc and cv/cv stacking, along with the doped cationic nitrogen atoms forming connecting nodes, which give rise to the distinctive “windmill-like” shape crystal structure. It is noteworthy that the solid-state architecture of 12a(2PF6–) is primarily built by the ionic bonds between cationic nitrogen and the PF6– counterions. Meanwhile, this special stacking arrangement opens up new possibilities for designing and synthesizing materials with distinctive properties that are seldom achieved in planar structures.82

Absorption and Emission Properties

To unravel the impact of both cationic nitrogen dopants and curved π-systems on the overall photophysical properties, UV–vis absorption and fluorescence spectra of compounds 9–12b in CH2Cl2 solutions were measured. The results are shown in Figure 5 and Table 1. Extended quinolizinium-fused corannulene derivatives 11a–12b exhibited similar UV–vis absorption maxima at λ = 310–315 nm, situated between that of pristine corannulene (254 nm)15 and diazapentabenzocorannulenium 4a (352 nm).48 Based on the absorption onsets, the optical energy gaps are estimated to range from 2.60 eV (11a) and 2.61 eV (11b) to 2.43 eV (12a) and 2.46 eV (12b), which suggests a reduced energy gap of dications (12a,b) than that of the singly charged derivatives (11a,b). In the emission spectra, 11a and 11b exhibited emission wavelength maxima at λ = 529 and 520 nm compared with the emission wavelength maxima of 12a and 12b at λ = 561 and 554 nm, respectively. This result reveals an obvious red shift compared with the emission maxima of corannulene (423 nm) and 4a (491 nm), which can be attributed to the peripherally π-extended cationic pyridinium/quinolizinium moieties. Notably, a 30 nm red shift was observed between singly charged derivatives (11a,b) and dications (12a,b), indicating that the doped cationic nitrogen atom could lower the optical energy gap of such a curved system. As reference, diaminocorannulene 9 displays maximum absorptions at λ = 254 and 294 nm and emission at λ = 521 nm, which are similar to those of 11a and 11b, suggesting that the introduction of two amino groups or a quinolizinium-fused moiety has comparable effects on altering the optical properties of corannulene. Dipyridocorannulene 10 shows UV absorption maxima at λ = 282 nm and emission wavelength maxima at 443 and 467 nm with an obvious blue shift compared with the cationic derivatives. All cationic corannulenes (11a–12b) have a large Stokes shift range from 1.3 to 1.4 × 104 cm–1. The fluorescence quantum yields (Φf) in CH2Cl2 solutions for these compounds vary from 6 to 31%, with compound 9 demonstrating the largest quantum yield (31%) because of the electron-donating effect of two amino groups. Compared with pristine corannulene, the quinolizinium-fused corannulenes 11a–12b exhibit enhanced solubility in various organic solvents. The incorporation of cationic nitrogen atoms enhances both solubility and fluorescence properties, endowing these curved PAH salts with potential for biological and supramolecular applications.83

Figure 5.

Figure 5

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(A) UV–vis absorption spectra of 9–12b in CH2Cl2. Inset right: Photographs of their CH2Cl2 solutions under visible (top) and UV (365 nm) light (bottom). (B) Normalized absorption (solid lines) and fluorescence (dashed lines) spectra of 9–12b in CH2Cl2.

Table 1. Photophysical Properties of 9–12b in CH2Cl2a.

  λabs (nm) λem (nm)b λex(max) (nm)c SSd Φf (%)
9 254, 294 521 305 2.0 31
10 282 443, 467 306 1.4 6
11a 256, 312 529 323 1.3 13
11b 310 520 369 1.3 11
12a 314 561 334 1.4 9
12b 315 554 338 1.4 10
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a

abs = absorption, em = emission, Φf = fluorescence quantum yield.

b

λem was measured with excitation wavelength at 360 nm.

c

λex(max) = excitation maxima.

d

SS = Stokes shift (×104 cm–1).

Electrochemistry

The electrochemical behavior of 10–12b was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Measurements were performed in degassed and dry THF using Bu4NPF6 as a supporting electrolyte and calibrated versus ferrocenium/ferrocene (Fc+/Fc). All curves are shown in Figures S4–S9, and the experimental data are summarized in Table S2.

As reference, the pyridine analogue 10 exhibited three reversible reduction waves at −2.21, −2.67, and −2.97 V. In contrast, the extended quinolizinium-fused corannulenes 11a–12b exhibited five reversible reduction waves (Table S2). Upon peripheral π-extension with cationic quinolizinium moieties, the first reduction potentials are significantly increased from 10 (two pyridine moieties, −2.21 V) to 11a/11b (one pyridine and one quinolizinium moiety, −1.09 V/–1.13 V) to 12a/12b (two quinolizinium moieties, −0.88 V/–0.89 V), suggesting a correlation between the reduction potential and the degree of doping with nitrogen cations. The experimental LUMO energy levels of 10–12b were estimated from the onset potentials of the first reduction waves to be −2.65, −3.77, −3.98, −3.72, and −3.97 eV, respectively. Accordingly, their experimental HOMO levels are calculated to be −5.96, −6.37, −6.33, −6.41, and −6.43 eV, respectively, based on the corresponding optical energy gaps. The calculated energies of the HOMO/LUMO level of 10–12b are in good accordance with the experimental data (Table 2).

Table 2. Electrochemical Property, Optical Gap, and Theoretical Calculation of Compounds 10–12b.

  Ere (onset)a ELUMOb (eV) EHOMOc (eV) optical gapd (eV) LUMOe (eV) HOMOe (eV) HOMO–LUMO gape (eV)
10 –2.15 –2.65 –5.96 3.31 –2.19 –6.27 4.08
11a –1.03 –3.77 –6.37 2.60 –3.51 –6.70 3.19
11b –1.08 –3.72 –6.33 2.61 –3.47 –6.66 3.18
12a –0.82 –3.98 –6.41 2.43 –4.27 –7.15 2.88
12b –0.83 –3.97 –6.43 2.46 –4.22 –7.10 2.89
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a

Onset value of the first reduction potentials obtained from CV.

b

The LUMO energy was calculated using the relation ELUMO = −(Ere(onset) vs Fc/Fc+ + 4.8) eV.

c

HOMO was estimated according to EHOMO = ELUMO + Eg.

d

Optical gap (Eg) was estimated from the UV–vis onset value.

e

Obtained from theoretical calculations at the B3LYP/6-311G (2d, p) level of theory.

The effects of doping cationic nitrogen on curved PAHs were further evaluated by DFT calculations at the B3LYP/6-311G (2d, p) level (Table 2 and Figures S12–S17). In comparison to neutral 10, the HOMO values of singly charged 11a/11b and doubly charged 12a/12b are lowered by 0.43/0.39 eV and 0.88/0.83 eV, and the LUMO values are lowered by 1.32/1.28 eV and 2.08/2.03 eV, respectively, indicating their enhanced electron-accepting properties. The band gaps are also lowered from 10 (4.08 eV) to 11a–12b (2.88–3.19 eV). In addition, the electron-donating n-butyl-substituted corannulenes 11b/12b present higher HOMO and LUMO values compared with the parent phenyl substituted corannulenes 11a/12a, which opens the possibility of tuning the electronic nature of such charged π-extended systems.

Conclusions

In conclusion, we have designed and synthesized four novel π-extended quinolizinium-fused corannulene derivatives 11a,b and 12a,b by employing a rationally designed synthetic strategy featuring a double Skraup–Doebner–Von Miller quinoline synthesis and rhodium-catalyzed CHAA as the key steps. In the solid state, the obtained 12a(2PF6–) exhibits an extended discoidal structure with an inversion barrier of 14.0 kcal/mol, which was confirmed by DFT calculations. Meanwhile, it stacks with a unique “windmill-like” repeating unit that is unusual compared to the packing behaviors of planar forms. Furthermore, UV–vis and fluorescence spectra reveal their enhanced fluorescence efficiency and large Stokes shift. Upon peripheral π-extension with cationic quinolizinium moieties, lower band gaps and higher electron affinity are introduced, implying their potential as (opto)electronic materials. In this work, the charged corannulene-based curved topology lays the foundation for the future construction of curved cationic nitrogen-doped nanocarbon materials.

Methods

General Information

Unless otherwise stated, all chemicals were of reagent grade or higher, obtained from commercial sources, and used without further purification. Flash chromatography was performed on silica gel 200–300 mesh or neutral Al2O3. Thin layer chromatography (TLC) was performed on glass-backed plates precoated with silica (GF254), which were developed using standard visualizing agents. 1H and 13C NMR spectra were recorded on a 400 or 600 MHz Bruker AVANCE spectrometer at 298 K. Chemical shifts (δ) are reported in ppm with the solvent resonance as the internal standard (CDCl31H: δ 7.26, 13C: δ 77.16). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, br = broad, m = multiplet), integration, and coupling constants (J) in Hz. IR absorption spectra were recorded using a Bruker Tensor II FTIR spectrometer (MCT detector, 4000–400 cm–1 range, resolution of 4 cm–1, averaging by 16 scans). Melting points were recorded on a national standard melting point apparatus without correction. High-resolution mass spectra (HRMS) were recorded for accurate mass analysis on a Q-TOF micro (Bruker Compass Data Analysis 4.0) spectrometer.

Photophysical and Electrochemical Methods

The UV absorption spectra were measured with an Agilent Cary 60 UV–vis spectrophotometer. Fluorescence excitation/emission measurements were carried out on an Edinburgh FLS980 spectrophotometer, using a 450 W xenon arc lamp, with excitation and emission slit widths at 1 nm. Absolute quantum yields were measured using an integrating sphere detector from Edinburgh Instruments. CV and DPV curves were recorded on a Shanghai Chenhua Instrument Co. Ltd. CHI660E Electrochemical Workstation.

X-ray Diffraction

A single crystal with dimensions 0.03 mm × 0.03 mm × 0.05 mm was selected and mounted in inert oil and then transferred to the cold gas stream of a Rigaku XtaLAB FRX diffractometer equipped with the Hypix6000HE detector. X-ray diffraction intensity data were recorded using mirror-focused Cu Kα radiation (λ = 1.54184 Å) and reduced by using the software package CrysAlisPro, applying an empirical absorption correction. The structure was solved by the intrinsic phasing method using the SHELXT84 structure solution program and then refined with the SHELXL84 refinement package using least-squares minimization in OLEX2.85

DFT Calculations

The computations were performed by using the Gaussian 16 (revision B.01) program86 by the B3LYP method with the 6-311G (2d, p) basis set for structure optimization, energy calculations (the counteranions were deleted and the solvation model was used with tetrahydrofuran), NICS,87 and ACID88 calculations. The geometry of planar TS was optimized without symmetry assumption, and IRC calculations were also performed to check the transition states.

Acknowledgments

The authors are grateful for the funding support from the National Program on the Key Basic Research Project of China (973 Program) (2015CB856500) and the National Natural Science Foundation of China (NSFC) (grant nos. 21672159 and 21871207). The Instrumental Analysis Center of SPST at Tianjin University is acknowledged for providing NMR, HRMS, and X-ray crystal diffraction analysis. The authors are further thankful to Andrew C. -H. Sue and Jay S. Siegel for their constructive comments and suggestions.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.4c00105.

  • Details of the synthesis and spectroscopic characterization of new compounds (PDF)

  • Crystallographic data (CCDC no.: 2326727), theoretical calculation, and electrochemical data (CIF)

Author Contributions

L.H. and J.H. conceived of the project. L.H. performed the experiments and data analysis. Q.W. executed all the theoretical calculations. P.F. performed the synthetic experiments. Y.S. analyzed the photophysical data. J.X. solved and refined the X-ray structures. L.H. wrote the original manuscript. D.L.B. and J.H. revised and edited the manuscript. J.H. acquired funding and supervised the project. All authors have given approval to the final version of the manuscript.

The authors declare no competing financial interest.

Supplementary Material

au4c00105_si_001.pdf (2.5MB, pdf)
au4c00105_si_002.cif (3.6MB, cif)

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