We describe an example of redox intercalation using vanadium benzenedicarboxylate, VOBDC as the host and electroactive hydroquinone as the guest. In our previous work, we synthesized single crystals of [VOBDC](H2BDC)0.71, 1 . After removal of the guest acid molecules by heating 1 in air, the VOBDC structure, 2 is sufficiently flexible and stable to undergo redox intercalation with hydroquinone. The reaction temperatures and especially the atmosphere were found to be the factors that determined the products. In ambient atmosphere, when 2 was heated together with hydroquinone, a quinhydrone complex formed inside the VOBDC channels, whereas under anhydrous conditions hydroquinone was found to functionalize the VOBDC framework itself, as shown in Figure 1. The products were characterized by single crystal X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and electron paramagnetic resonance spectroscopy (EPR). According to EPR studies, the product from the anhydrous reaction was found to contain unpaired electrons. The effect of changing the temperature from 298 K to 100 K on the breathing transitions of the framework will be described. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/240nm/uploads/43365_acs_fall_2010-figure.jpg' alt='' /> Figure 1 (a) View along the b-axis of VOBDC. (b) Single chain of VO6 octahedra. (c) Reaction of VOBDC with hydroquinone: oxygen in red and vanadium in green.

Redox intercalation of hydroquinone into a flexible metal-organic framework

247th National Meeting (2014)

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