journal article·2022-04Open access

Monolayer nanoarchitecture of crystalline metallopolymers by electrochemical iterative growth

Jinxin Wang, Chang Wei, Shumu Li, Qi Hao, Jie Shi, Jianan Liu, Lin Li, Yuannan Chen, Yanfang Wang, Yongfang Li, Lingyun Shen, Xinbo Zhang, Wenjing Hong, Mao Li

Cell Reports Physical Science· Volume 3· Issue 4

Abstract

The assembly of oriented molecular nanoarchitecture by controlled manipulation on a molecule-by-molecule basis is desirable for molecular materials and electronics. However, this nanoarchitecture of polymers is hampered by kinetic and statistical restrictions during polymer synthesis and manipulation. Here, we report the monolayer nanoarchitecture of long-range crystalline metallopolymers in vertical arrays, with heights ranging from 2 to 30 nm on conductive substrates, via kinetically accelerated and statistically allowed iterative growth, guided by a self-assembled monolayer with monitoring and defect-repair abilities. The monolayer shows a surface roughness of 0.65 nm, a theoretically highest density of 0.79 chains/nm2, and superior tailoring in conductance and electrocatalysts as a function of height with very low decay constants in the electron transport of 0.063 nm−1. Highly controlled synthesis for engineering standard functional polymer monolayers with a uniformity in single monomer precise can present superior structure and function in contrast to conventional SAMs based on small molecules.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Conducting polymers and applications · Polymer Surface Interaction Studies · Fuel Cells and Related Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (34)

Show source-provided references
1. Brush-modified materials: control of molecular architecture, assembly behavior, properties, and applications10.1016/j.progpolymsci.2019.101180 ↗
2. Surface chemical reactions on self-assembled silane based monolayers10.1039/D0CS01220C ↗
3. Large-area, ensemble molecular electronics: motivation and challenges10.1021/acs.chemrev.6b00595 ↗
4. Self-assembled monolayers in organic electronics10.1039/C6CS00509H ↗
5. Surface-initiated controlled radical polymerization: state-of-the-art, opportunities, and challenges in surface and interface engineering with polymer brushes10.1021/acs.chemrev.6b00314 ↗
6. “Grafting through”: mechanistic aspects of radical polymerization reactions with surface-attached monomers10.1021/ma402607d ↗
7. Interfacial synthesis of electrofunctional coordination nanowires and nanosheets of bis(terpyridine) complexes10.1016/j.ccr.2017.02.013 ↗
8. Ultrastable glassy polymer films with an ultradense brush morphology10.1021/acsnano.0c09631 ↗
9. Polymer on top: current limits and future perspectives of quantitatively evaluating surface grafting10.1002/adma.201706321 ↗
10. New methods in polymer brush synthesis: non-vinyl-based semiflexible and rigid-rod polymer brushes10.1016/j.progpolymsci.2021.101361 ↗
11. Layer-by-layer assemblies of coordinative surface-confined electroactive multilayers: zigzag vs orthogonal molecular wires with linear vs molecular sponge type of growth10.1021/acs.jpcc.7b10900 ↗
12. Highly conductive ∼40-nm-long molecular wires assembled by stepwise incorporation of metal centers10.1038/nmat2332 ↗
13. Electrochemical-coupling layer-by-layer (ECC–LbL) assembly10.1021/ja202768k ↗
14. Electrochemical nanoarchitectonics and Layer-by-Layer assembly: from basics to future10.1016/j.nantod.2015.02.008 ↗
15. Schubert · 2021
16. Metallopolymers: new multifunctional materials10.1002/adma.200702876 ↗
17. Functional soft materials from metallopolymers and metallosupramolecular polymers10.1038/nmat2966 ↗
18. Transition metal-containing macromolecules: en route to new functional materials10.1016/j.polymer.2012.08.024 ↗
19. Supramolecular metallopolymers: from linear materials to infinite networks10.1002/anie.201806912 ↗
20. Recent trends in metallopolymer design: redox-controlled surfaces, porous membranes, and switchable optical materials using ferrocene-containing polymers10.1002/chem.201800412 ↗
21. Surface-immobilized conjugated polymers incorporating rhenium bipyridine motifs for electrocatalytic and photocatalytic CO2 reduction10.1021/acsaem.8b01745 ↗
22. Electropolymerized films of vinyl-substituted polypyridine complexes: synthesis, characterization, and applications10.1016/j.ccr.2013.01.001 ↗
23. Electrocatalytic reduction of carbon dioxide to carbon monoxide by a polymerized film of an alkynyl-substituted rhenium(I) complex10.1002/cctc.201200904 ↗
24. Controlled electropolymerization based on self-dimerizations of monomers10.1016/j.coelec.2022.100952 ↗
25. Photophysics of π-conjugated polymers that incorporate metal to ligand charge transfer chromophores10.1021/ja963278t ↗
26. Defining the value of injection current and effective electrical contact area for EGaIn-based molecular tunneling junctions10.1021/ja408652h ↗
27. Noncovalent self-assembled monolayers on graphene as a highly stable platform for molecular tunnel junctions10.1002/adma.201504207 ↗
28. Electrical resistance of long conjugated molecular wires10.1126/science.1156538 ↗
29. Achieving ultralow, zero, and inverted tunneling attenuation coefficients in molecular wires with extended conjugation10.1002/smll.202005711 ↗
30. Comparison of DC and AC transport in 1.5-7.5 nm oligophenylene imine molecular wires across two junction platforms: eutectic Ga-In versus conducting probe atomic force microscope junctions10.1021/jacs.6b02039 ↗
31. Transition from tunneling to hopping in single molecular junctions by measuring length and temperature dependence10.1021/ja1040946 ↗
32. Single-molecule electrical detection: a promising route toward the fundamental limits of chemistry and life science10.1021/acs.accounts.9b00347 ↗
33. Rhenium chemistry–then and now10.1016/j.ccr.2021.213822 ↗
34. Photoelectrochemical CO2 reduction with a rhenium organometallic redox mediator at semiconductor/aqueous liquid junction interfaces10.1002/anie.201908398 ↗