Amorphous covalent inorganic-organic hybrid frameworks (CIOFs) with an aggregation induced selective response to UV-visible light and their DFT studies

Covalent inorganic-organic hybrid frameworks (CIOFs) comprised of inorganic heterocycles covalently linked to organic building blocks are a relatively unexplored and fertile area of research compared to the covalent organic frameworks. Herein, we report selective light responsive CIOFs prepared by considering energy gaps (Egs) of inorganic heterocycle (P3N3Cl6) (Eg 5.745 eV), organic building block (4,4-sulfonyldiphenol) (Eg 4.05 eV), and triazine heterocycle (1,3,5-Triazine-2,4,6-triamine) (Eg 4.79 eV) under mild reaction conditions (by P-O-C and P-NH-C bond formation). The morphology of CIOF-I (prepared from hexachlorocyclotriphosphazene and 4,4-sulfonyldiphenol) is micro-spherical (diameter, ca. 0.6-1 μm), whereas CIOF-II (prepared from hexachlorocyclotriphosphazene and 1,3,5-triazine-2,4,6-triamine) is also micro-spherical (diameter, ca. 0.5-1 μm) as well as tubular. The X-ray diffraction (XRD) analysis showed that these CIOFs are amorphous in nature. The luminescence studies of both CIOFs have shown selective responses to different light. Under 365 nm of excitation wavelength, the CIOFs showed cyan emission, while under visible region 420 nm and 546 nm excitation, emission shift to green and red, respectively. CIOF-I demonstrated maximum emission at 454 nm (Ex. 365 nm), 487 nm (Ex. 420 nm), and 708 nm (Ex. 546 nm), while CIOF-II has shown maximum emission at 460 nm (Ex. 365 nm), 478 nm (Ex. 420 nm), and 604 nm (Ex. 546 nm), respectively. The density functional theory (DFT) studies were performed on Gaussian 09 (B3LYP/6–311+G (d,p)) for the core structure of CIOFs HOMO and LUMO levels (CIOF-I -6.54 eV, -2.62 eV and CIOF-II -6.44 eV, -2.55 eV) and Egs (3.92 eV and 3.84 eV) which are in good agreement with the experimental values. The mechanism behind two different chemical structures demonstrated similar emission colors are also underpinned. The selective response towards different lights is ascribed to the aggregation/clusterization-induced/triggered emission (AIE/CTE) and restricted rotation emission (RRE) due to the crosslinking of the wider energy gap inorganic heterocycle and organic linkers. This study may grab the attention of researchers to study inorganic heterocycles centered selective light responsive materials for extensive application prospects.