A contorted nanographene shelter

Nanographenes have kindled considerable interest in the fields of materials science and supramolecular chemistry as a result of their unique self-assembling and optoelectronic properties. Encapsulating the contorted nanographenes inside artificial receptors, however, remains challenging. Herein, we report the design and synthesis of a trigonal prismatic hexacationic cage, which has a large cavity and adopts a relatively flexible conformation. It serves as a receptor, not only for planar coronene, but also for contorted nanographene derivatives with diameters of approximately 15 Å and thicknesses of 7 Å. A comprehensive investigation of the host-guest interactions in the solid, solution and gaseous states by experimentation and theoretical calculations reveals collectively an induced-fit binding mechanism with high binding affinities between the cage and the nanographenes. Notably, the photostability of the nanographenes is improved significantly by the ultrafast deactivation of their excited states within the cage. Encapsulating the contorted nanographenes inside the cage provides a noncovalent strategy for regulating their photoreactivity.


S4
rotary evaporation under vacuum. The residue was then treated with an excess of NH4PF6, resulting in a red precipitate, which was separated by filtration and dried under vacuum yielding TPACage•6PF6 (yield: 30%). 1  using an injection pump. The resulting solution was followed by the dropwise addition of a solution of 1,3,5-tris(3,4-dimethoxybenzyl)benzene (TBB，0.5 mmol, 264 mg) in CH2Cl2 (50 mL) over 1 h. The mixture was stirred at room temperature overnight. The remaining FeCl3 solution in MeNO2 (20 mL) was added dropwise to the reaction mixture over 1 h. After continuing to stir for 12 h under a N2 atmosphere, cold MeOH (100 mL) was added to quench the reaction and the mixture was poured into cold H2O (500 mL). The aqueous layer was extracted with CH2Cl2 (3  100 mL).

S26
(2) High-resolution mass spectrometry (HRMS) of the four host-guest complexes In the mass spectra of four host-guest complexes (Supplementary Figs. 4245), signals for free host cage, i.e., m/z = 427.65, m/z = 618.53 were also observed as a result of the dissociation of the complexes during mass spectrometric measurements. The blue "4+" and "3+" represent the four and three positively charged states of the free TPACage•6PF6, while the brown "5+" "4+"and "3+" represent the five, four and three positively charged states of the host-guest complexes, respectively.        The solution was passed through a 0.45-μm filter and added to two 1-mL tubes with the volume of 0.30 and 0.70 mL, respectively. The tubes were placed together in one 20-mL vial without capping.

S39
The yellow single crystals of 3H-HBC were obtained by slow evaporation over the course of five days. A single crystal was mounted on a MITIGEN holder in Paratone oil on a XtaLAB Synergy R, DW system, HyPix diffractometer. The crystal was kept at 100.01 K during data collection.
Using Olex2 3 , the structure was solved with the ShelXT 4 structure solution program using Intrinsic Phasing and refined with XL 5 refinement package using Least Squares minimization. The solidstate structure of 3H-HBC is shown in Fig. 3e.   Using Olex2 3 , the structure was solved with the XT 4 structure solution program using Intrinsic Phasing and refined with the XL 5 refinement package using Least Squares minimization. The solidstate superstructure of COR⊂TPACage•6Cl is shown in Fig.6 and Supplementary Fig. 65. (c) Refinement Details. Distance restraints were imposed on the disordered COR. The enhanced rigid-bond restraint was applied to the COR as well as restraints on similar amplitudes (esd 0.05) separated by less than 1.7 Å and restraints that its Uij components approximate to isotropic.   The cavity volume of TPACage 6+ was calculated using a 3V channel program 6 . The volume was probed by taking the difference between two rolling-probe solvent-excluded surfaces, one with as large as possible a probe radius and the other with a small solvent radius. The small probe size was set at 1.4 Å while the big probe size was set as 10.0 Å.

Supplementary Figure 68. Space-filling (a) and capped-stick (b) representation of TPACage 6+
showing the inner volume (yellow filling, 368 Å 3 ). The volume was calculated by using a virtual rolling probe with a 1.4 Å radius.

(2) Visualization of noncovalent interactions
Independent gradient model (IGM) analysis is an approach 7 based on promolecular density (an electron density model prior to molecule formation) to identify and isolate intermolecular interactions. Strong polar attractions and van der Waals contacts are visualized as an iso-surface with blue and green color, respectively. Single crystal superstructures were used as input files. The

(4) Frontier molecular orbital calculations
The xyz coordinates from the X-ray single crystals structures were used as the starting geometries

(5) Electrostatic potential map calculations
The electrostatic potential maps were computed with B3LYP, the Slater-type basis set 24         . (a) FsTA Spectra at selected delay times, (b) species associated spectra, and (c) fits to kinetic model S * 1 → S1 → S0 at selected wavelengths obtained using global analysis. S * 1, S1, and S0 represent the vibrationally-hot first singlet excited state, first singlet excited state, and ground state of TPACage 6+ , respectively.