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Heterometallic Benzenehexathiolato Coordination Nanosheets: Periodic Structure Improves Crystallinity and Electrical Conductivity.

Published version
Peer-reviewed

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Type

Article

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Authors

Toyoda, Ryojun 
Fukui, Naoya 
Tjhe, Dionisius HL 
Selezneva, Ekaterina 
Maeda, Hiroaki 

Abstract

Coordination nanosheets are an emerging class of 2D, bottom-up materials having fully π-conjugated, planar, graphite-like structures with high electrical conductivities. Since their discovery, great effort has been devoted to expand the variety of coordination nanosheets; however, in most cases, their low crystallinity in thick films hampers practical device applications. In this study, mixtures of nickel and copper ions are employed to fabricate benzenehexathiolato (BHT)-based coordination nanosheet films, and serendipitously, it is found that this heterometallicity preferentially forms a structural phase with improved film crystallinity. Spectroscopic and scattering measurements provide evidence for a bilayer structure with in-plane periodic arrangement of copper and nickel ions with the NiCu2 BHT formula. Compared with homometallic films, heterometallic films exhibit more crystalline microstructures with larger and more oriented grains, achieving higher electrical conductivities reaching metallic behaviors. Low dependency of Seebeck coefficient on the mixing ratio of nickel and copper ions supports that the large variation in the conductivity data is not caused by change in the intrinsic properties of the films. The findings open new pathways to improve crystallinity and to tune functional properties of 2D coordination nanosheets.

Description

Funder: White Rock Foundation


Funder: Jardine Foundation


Funder: Cambridge Commonwealth European and International Trust

Keywords

2D polymers, benzenehexathiolato metal complexes, coordination nanosheets, electrical conductivities, heterometallicity

Journal Title

Adv Mater

Conference Name

Journal ISSN

0935-9648
1521-4095

Volume Title

Publisher

Wiley
Sponsorship
The Royal Society (nf121150)
Engineering and Physical Sciences Research Council (EP/P007767/1)
Engineering and Physical Sciences Research Council (EP/S030662/1)
Engineering and Physical Sciences Research Council (EP/P024947/1)
Engineering and Physical Sciences Research Council (EP/S019367/1)
Engineering and Physical Sciences Research Council (EP/R00661X/1)
EPSRC-JSPS core-to-core program (EP/S030662/1, JPJSCCA20190005)