Metal−organic coordination polymers (CPs) downsized to thin films with controllable electrical conductivity are promising for electronic device applications. Here we demonstrate, for the first time, thermally driven resistive switching in thin films of semiconducting CPs consisting of silver ion and tetracyanoquinodimethane ligand (AgTCNQ). High-quality and highly hydrophobic thin films of Ag-TCNQ were fabricated through a layer-by-layer approach upon sacrificing a pre-deposited layer of Cu-TCNQ on a thiolated Au substrate. Reversible switching between the high-resistance state (HRS) at 300 K and the low-resistance state (LRS) at 400 K with an enhancement factor of as high as ∼10 6 in the electrical resistance was realized. The phenomenon is attributed to the alternation of the Schottky barrier at the metal−semiconductor interface by thermal energy and not due to the formation of a conductive filament. Our discovery of thermally driven resistive switching as well as sacrificial growth of CP thin films on an organically modified substrate holds promise for the development of solution-processable non-volatile memory devices.

In this work we report fabrication of high-quality AB- and BA-type heterostructured thin films of cubic Cu­(II) (A-type) and tetragonal Cu­(I) (B-type) coordination polymers (CPs) on the functionalized Au substrate by the layer-by-layer method. Successful growth of Cu­(I)-CP on top of Cu­(II)-CP was assigned to be due to the interfacial reduction reaction (IRR). Notably, electrical transport measurements across AB- and BA-type heterostructured thin films revealed rectification of current in opposite directions. We have attributed such an interestingly new observation to the formation of a well-defined interface of Cu­(II)-CP and Cu­(I)-CP resembling a p–n junctiona hitherto unreported phenomenon that is anticipated to open enormous opportunities for the heterostructured thin films of CPs, likewise celebrated interfaces of oxide heterostructures.

Oxidation and reduction reactions are of central importance in chemistry as well as vital to the basic functions of life and such chemical processes are generally brought about by oxidizing and reducing agents, respectively. Herein, we report the discovery of an interfacial reduction reaction (IRR) − without the use of any external reducing agent. In course of metal−ligand coordination, spontaneous reduction of Cu(II) to Cu(I) at a solid−liquid interface was observed−unlike in a liquid-phase reaction where no reduction of Cu(II) to Cu(I) was occurred. High-quality thin films of a new coordination network compound bearing a Fe(II)−CN−Cu(I) link were fabricated by IRR and employed for efficient electro-catalysis in the form of oxygen reduction reaction. Also, thermally activated reversible structural phase transition modulated the electron transport property in thin film. This work unveils the importance of chemical reactions at solid−liquid interfaces that can lead to the development of new functional thin film materials.

A record value of the current rectification ratio (RR ≥ 105) across molecularly doped thin films of a Cu(ii)-coordination polymer is achieved.

Wet-chemical fabrication of a crystalline Ag-TCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) thin film on non-Ag substrate is challenging whereby the chemistry was powered by photon energy and/or electrical energy. We report for the first time, direct chemical growth of a Ag-TCNQ thin film on a functionalized Au substrate by employing the layer-by-layer (LbL) approach at ambient reaction conditions. Various Ag­(I) salt precursors previously realized to be unsuitable for the fabrication of Ag-TCNQ thin films on non-Ag substrates ultimately gave rise to dense and uniform thin films of Ag-TCNQ. The crucial knob regulating the direct formation of the thin films of Ag-TCNQ was identified to be the pH of the respective Ag­(I) solutions.