Photoswitchable Fluorescent Self-Assembled Metallacycles with High Photostability.

In this study, photoswitchable fluorescent supramolecular metallacycles with high fatigue-resistance have been constructed by coordination-driven self-assembly by using bithienylethene with dipyridyl units (BTE) as a coordination donor and a fluorescent di-platinum(II) (Pt-F) as a coordination acceptor. The photo-triggered reversible transformation between the ring-open and ring-closed form of the metallacycles was confirmed by 1 H NMR, 31 P NMR, and UV/Vis spectroscopy. This unique property enabled a reversible noninvasive "off-on" switching of fluorescence through efficient Förster resonance energy transfer (FRET). Importantly, the metallacycles remained structurally intact after up to 10 photoswitching cycles. The photoresponsive property and exceptional photostability of the metallacycles posit their potential promising application in optical switching, image storage, and super-resolution microscopy.

Enabling Light Work in Helical Self-Assembly for Dynamic Amplification of Chirality with Photoreversibility.

Light-driven transcription and replication are always subordinate to a delicate chirality transfer. Enabling light work in construction of the helical self-assembly with reversible chiral transformation becomes attractive. Herein we demonstrate that a helical hydrogen-bonded self-assembly is reversibly photoswitched between photochromic open and closed forms upon irradiation with alternative UV and visible light, in which molecular chirality is amplified with the formation of helixes at supramolecular level. The characteristics in these superhelixes such as left-handed or right-handed twist and helical length, height, and pitch are revealed by SEM and AFM. The helical photoswitchable nanostructure provides an easily accessible route to an unprecedented photoreversible modulation in morphology, fluorescence, and helicity, with precise assembly/disassembly architectures similar to biological systems such as protein and DNA.