The synthesis of electrode-attached Rh(I) diisocyanide coordination polymers that incorporate a series of arylene diisocyanide linkers and which are grown from gold surfaces by a bottom-up, layer-by-layer procedure that allows for a high level of control for the film thickness is reported. A seed layer of the arylene diisocyanide ligand is used to template directional growth of the coordination polymer made using the well-studied square-planar rhodium tetrakis(isocyanide) as the metal node. Materials ranging from 1 to 30 layers were prepared via layer-by-layer solution-phase deposition. Characterization of the polymer films using scanning electron microscopy and ellipsometry shows layer-by-layer control in these films with linear thickness growth per layer. Phasemodulated infrared reflection absorption spectroscopy (PM-IRRAS), diffuse reflectance UV−vis, and X-ray photoelectron spectroscopy (XPS) were used to confirm the structures of the films. Although prior reports of related coordination polymers and films based on diisocyanides showed considerable air-instability, the films reported here demonstrate significantly improved chemical stability and electrochemical stability at a moderately high applied bias. Electrochemical characterization and ex situ XPS demonstrate that these diisocyanide films are stable to stripping at potentials up to −2.2 V versus decamethylferrocene in acetonitrile, supporting their relevance for electrochemical applications.
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Designing hierarchical structures of complex electronically conducting organic polymers via one-step electro-polymerization
Thermal chemical synthesis of conjugated polymers has often been plagued by low product yields, by-product contamination and high-cost catalysts. Electrochemical synthesis is an alternative strategy that can overcome these failures to obtain highly efficient syntheses. Herein, we present the study of diketopyrrolopyrrole-bisthiophene (DPPT 2 ), diketopyrrolopyrrole-bisfuran (DPPF 2 ) and thienothiadiazole-bisthiophene (TTDT 2 ) for diblock copolymerization with terthiophene (T 3 ) as a π-linker to form tunable narrow band gap polymers. The polymers suspended as thin films have similar redox characteristics to the monomers with potential shifts that prove the identity of the respective polymers. Electrochemical impedance measurements were carried out in the −0.6 V to 1.0 V potential range with an average electron transport resistance ( R e ) value of 110 Ω irrespective of the applied potential. This confirms the polymers to have higher intrinsic electrical conductivity. The atomic ratios of the synthesized materials were calculated experimentally using energy dispersive X-ray (EDX) analysis, and they confirm the theoretical composition of the polymers. These doped polymers exhibit absorption bands in the visible to SWIR region (800–1800 nm) with optical band gaps from 0.773 to 1.178 eV in both the solid and the solution state.
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- Award ID(s):
- 1757220
- PAR ID:
- 10166244
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 8
- Issue:
- 17
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 5934 to 5940
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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