The incorporation of photochromic moieties into porous coordination polymers is of particular interest due to it can endow them various switchable functions in the electrical conductivity, luminescence, and magnetism. In...

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As an emerging class of hybrid complexes, the donor-acceptor (D-A) hybrid heterostructures combined with both advantages of photoactive organic and inorganic components have provided an excellent platform for the fabrication...

Donor−acceptor (D−A) hybrid crystals are an emerging kind of crystalline hybrid material composed of semiconductive inorganic donors and organic acceptors. Except for the intrinsic photochromism, recently we have reported that the anion-π polyoxometalate (POM)/naphthalenediimide (NDI) hybrid crystals could produce an interesting room temperature phosphorescence (RTP) quantum yield up to 7.2%. Herein, we extended into coresubstituted NDIs and anticipated the regulation of their photochromic and RTP properties. Thus, two hybrid crystals, namely (H 4 BDMPy-Br 2 NDI)•(NMP) 4 •(HPW 12 O 40 ) (1) and (H 4 BDMPy-I 2 NDI)• (HPW 12 O 40 ) (2) (H 2 BDMPy-Br 2 NDI: N,N′-bis(3,5-dimethylpyrazolyl)-2,6-dibromo-1,4,5,8-naphthalenediimide and H 2 BDMPy-I 2 NDI: N,N′-bis(3,5-dimethylpyrazolyl)-2,6-diiodide-1,4,5,8-naphthalenediimide), have been synthesized from phosphotungstic anions (PW 12 O 40 3− ) and Br or I core-substituted NDIs. Compared to the coreunsubstituted analogues (H 4 BDMPy-NDI)•(NMP) 4 •(HPW 12 O 40 ) ( 3), 2 with photosensitive iodine substituents is more sensitive to light, which can become discolored under natural light. As a result of the heavy-atom effect, hybrid 1 exhibits remarkable RTP with the quantum yield up to 10.2% and a lifetime of 1.14 ms.

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