To overcome one of the disadvantages of most coordination polymers and metal–organic frameworks (MOFs) being insulators, conjugated coordination polymers are investigated regarding their electrical conductivity. Rhodium paddlewheel units containing coordination polymers are synthesized as bulk. They are deposited on functionalized gold substrates via a layer-by-layer approach using a self-built dip-coater. For the detailed characterization of topography and conductivity, atomic force microscopy (AFM) is used. The exchange of the equatorial coordinated acetates with acetamides leads to a change from insulating to semiconducting behavior. A temperature dependence of the current, more precisely, an increase of current with increasing temperature, is observable. The determined activation energy is between 0.3 and 0.5 eV. Bulk-limitation of charge transport is observed, and related hopping mechanisms are discussed. Conductive AFM allows us to characterize conductive coordination polymers and MOFs for a later potential usage in sensor devices.

The controlled growth of surface‐modifying polymer films by electrodeposition often fails because of the lack of redox activity of these compounds. Here, electroactive complexants help to electrodeposit non‐electroactive polymers. Hence, we investigate the counterion‐induced electrodeposition of polyelectrolytes: three quaternized poly(N,N‐dialkylaminoethyl methacrylate)s (qPDAAEMA), in particular their methyl, ethyl, and isopropyl derivatives (i. e. qPDMAEMA, qPDEAEMA, and qPDPAEMA), provide transparent solutions in the presence of hexacyanoferrate(II) (ferrocyanide) at specific concentration windows of the KCl supporting electrolyte. Below a certain KCl concentration, insolubility dominates irrespective of the hexacyanoferrate valency, whilst above an upper threshold, full solubility is observed. Between these limits, oxidation reversibly electrodeposits polymer/hexacyanoferrate(III) (ferricyanide) complexes. Hydrodynamic voltammetry (and data analysis using in‐house software) provides access to the deposition efficiency (DE). qPDEAEMA with ethyl substituents shows highest DEs; larger or smaller substituents fall short because of a balance between “hydrophobicity” and charge separation, shifting the window toward smaller salt concentrations with increasing alkyl size. We always observe a DE maximum close to the minimum salt concentration, whilst electrochemical quartz crystal microbalance (EQCM) measurements indicate a change in film water content close to the maximum. These effects, being also discussed in terms of polymer conformation, can direct the future engineering of electroassisted coatings.

Surface-directed and preferentially oriented assemblies of nanomaterials can enable enhanced applications in e.g. catalysis or sensing. Coordination polymers, which can be even conducting, could be suitable materials for this purpose...