Abstract
Coordination polymerization leads to various metal–organic frameworks (MOFs) with unique physical properties and chemical functionalities. One of the challenges towards their applications as porous materials is to make MOFs optimally conductive to be used as electronic components. Here, it is demonstrated that Co-MOF-74, a honeycomb nano–framework with one–dimensionally arranged cobalt atoms, advances its physical properties by accommodating tetracyanochinodimethan (TCNQ), an acceptor molecule. Strong intermolecular charge transfer reduces the optical band gap down to 1.5 eV of divalent TCNQ and enhances the electrical conduction, which allows the MOF to be utilized for resistive gas- and photo-sensing. The results provide insight into the electronic interactions in doped MOFs and pave the way for their electronic applications.
Highlights
Metal–organic frameworks (MOFs)[1, 2] are exciting materials due to their unprecedented nanostructures that can be tailored on a bulk scale by linking designated metal ligands and organic molecules
We synthesize Co-metal–organic frameworks (MOFs)-74 in different forms as nanocrystalline, microcrystalline assemblages and as thin films, which we show to be successfully doped by TCNQ
A bright field (BF) transmission electron microscopy (TEM) image of nanocrystalline Co-MOF-74 in Fig. 2a shows the assemblage of individual nanoparticles into larger agglomerates (50–180 nm)
Summary
We synthesize Co-MOF-74 in different forms as nanocrystalline, microcrystalline assemblages and as thin films, which we show to be successfully doped by TCNQ. This is in contrast to the case of TCNQ−/Cu(100)[36] and lithium-intercalated TCNQ37, in which the main peak is shifted towards a lower binding energy and the shake-up feature suppressed Both observations are attributed to the addition of one electron. This is fully consistent with an optical absorption gap of about 1.5 eV.
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