Porous Pyrene Organic Cage with Unusual Absorption Bathochromic-Shift Enables Visible Light Photocatalysis

Abstract

We have constructed a novel porous pyrene-based organic cage, PyTC1, through the condensation reaction of cyclohexanediamine with 5,5′-(pyrene-1,6-diyl) diisophthalaldehyde. Single-crystal X-ray diffraction analysis reveals the effective intercage C-H ... π interaction between cyclohexanediimine and pyrene segments. Such a soft intercage C-H ... π interaction, rather than a classic J-aggregate with slipped π-π-stacking configuration, induced an unusual bathochromic shift of pyrene-based chromophore absorption from an ultraviolet region of PyTC1 in solution to the visible light region of PyTC1 in solid-state. This enabled heterogeneous visible light photocatalysis of aerobic hydroxylation of benzeneboronic acid derivatives. To the best of our knowledge, this is the first report that represents an absorption bathochromic shift caused by C-H ... π interaction. Such phenomenon could endow visible-light-driven photocatalysis that originally could only be achieved using UV light with the same chromophore.

Substituents make a difference: 6,6″-modified terpyridine complexes with helix configuration and enhanced emission

“…As displayed in Fig. 7B, L1 2 -Zn exhibited the emission peak at 405 nm with a noticeable bathochromic shift in comparison with that in solution, which was presumably due to C–H⋯π interaction 60 and supported by the crystal structures of a previous report. 43 In sharp contrast, a slightly blue-shifted emission was observed for L2 2 -Zn in solid compared with that of the solution samples (Fig.…”

Identification of Photocatalytic Alkaloids from Coptidis Rhizome by an Offline HPLC/CC/SCD Approach

“…In recent years, catalyzed synthesis using different Lewis acids as the catalysis, e.g., SnCl 2 , appeared to improve the yield [ 20 ]. Visible light as a convenient and renewable clean energy source has attracted increasing interest in organic photosynthesis [ 21 ]. Compared with traditional synthesis and heavy metal catalysis, visible light catalysis meets the requirements of green chemistry and environmental friendliness.…”

Self-assembled supramolecular materials for photocatalytic H2 production and CO2 reduction

“…These values are comparable to the highest ones reported for cobalt/ fluorescein systems, demonstrating the potential advantage of the supramolecular system in photocatalytic hydrogen production. Recently, Wang, Zhang, Jiang and coworkers reported a porous pyrene-based organic cage which displays heterogeneous photocatalysis of aerobic hydroxylation of benzeneboronic acid derivatives [53].…”