The contradiction between the rising demands of optical chirality sensing and the failure in chiral detection of cryptochiral compounds encourages researchers to find new methods for chirality amplification. Inspired by planar chirality and the host–guest recognition of pillararenes, we establish a new concept for amplifying CD signals of cryptochiral molecules by pillararene host–guest complexation induced chirality amplification. The planar chirality of pillararenes is induced and stabilized in the presence of the chiral guest, which makes the cryptochiral molecule detectable by CD spectroscopy. Several chiral guests are selected in these experiments and the mechanism of chiral amplification is studied with a non‐rotatable pillararene derivative and density functional theory calculations. We believe this work affords deeper understanding of chirality and provides a new perspective for chiral sensing.
Visible-light photosensitizers have emerged as a sustainable and environmentally friendly medium for organic transformation. Herein, we have developed a supramolecular strategy for manipulating visible-light photosensitization and photocatalytic efficiencies. With the elaborate manipulation of aggregated Pt(II)···Pt(II) interactions, the discrete tetranuclear Pt complexes not only show high binding affinity (K a ∼ 106 M–1) but also feature bathochromic-shifted metal–metal-to-ligand charge transfer transitions. Both factors are crucial for their 1O2 generation capability upon low-energy visible-light irradiation (λ ≥ 590 nm). More interestingly, when a terpyridine moiety is embedded in the structure of a supramolecular photosensitizer, breakup of tetranuclear Pt(II)···Pt(II) complexation can be realized upon addition of Zn(OTf)2. As a consequence, photo-oxidation of a secondary amine to the corresponding imine can be deactivated and reactivated, via the sequential addition of Zn(OTf)2 and unsubstituted terpyridine as the competitive ligand. Hence, the current study proves that intelligent visible-light photocatalysts can be achieved via rational supramolecular design.
Conspectus Platinum(II) terpyridine complexes have received tremendous attention in recent years because of their square-planar geometry and fascinating photophysics. Bottom-up self-assembly represents an intriguing approach to construct well-ordered supramolecular architectures with tunable optical and electronic properties. Until now, much effort has been devoted to the fabrication of monocomponent platinum(II) terpyridine-based assemblies. The next step is to develop multicomponent coassembled systems via the combination of platinum(II) terpyridine complexes with other π-organic and -organometallic molecules. The implementation of electron/energy transfer processes renders advanced functionality to the resulting coassemblies. For the fabrication of discrete multicomponent architectures, a feasible protocol is to construct preorganized molecular tweezers and macrocycles with the involvement of platinum(II) terpyridine complexes as the panel units. In view of their planar surface and positively charged character, such supramolecular receptors are capable of encapsulating electron-rich polyaromatic hydrocarbons and organometallic guests via donor–acceptor charge-transfer and/or metal–metal interactions. Intermolecular hydrogen bonds can be further incorporated between the molecular tweezers receptor and the polyaromatic hydrocarbon guests, giving rise to the strengthened binding affinity and sensitive stimuli-responsiveness. On this basis, multilayer donor–acceptor stacks have been obtained via the precise control over the number of pincers, which feature enhanced complexation strength and superior functionality. Moreover, platinum(II) terpyridine-based macrocycles are more suitable for guest accommodation than the corresponding molecular tweezers receptors in light of their definite size and constrained environment. Stimuli-responsive elements can be conveniently implemented into the rigid spacers of the molecular tweezers and macrocyclic receptors, facilitating the capture and release of the sandwiched guests in a highly controlled manner. On the other hand, long-range-ordered supramolecular polymers have been successfully fabricated with linear, hyperbranched, and cross-linked topologies by employing platinum(II) terpyridine-based molecular tweezers/guest recognition motifs as the non-covalent connecting unit. The degree of polymerization of the resulting donor–acceptor-type supramolecular polymers can be efficiently modulated by incorporating intermolecular hydrogen bonds between the molecular tweezers receptor and the complementary guest unit. An alternative approach toward extended multicomponent donor–acceptor assemblies is to mimic the structure of Magnus’ green salt. A delicate balance of non-covalent driving forces between homo- and heterocomplexation processes and a deeper understanding of thermodynamic and kinetic behaviors play the decisive roles in the final arrangement of the coassembled structures. Overall, multicomponent coassembly of platinum(II) terpyridine complexes into well-ordered na...
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