A New Charge-Ordered Molecular Conductor: κ-(BEDT-TTF)2K+(18-crown-6)[CoII(NCS)4]∙(H2O)

A new molecular conductor, i.e., κ-(BEDT-TTF)2K+(18-crown-6)[CoII(NCS)4]∙(H2O), is semiconductive with substantial charge gap values (ΔE) of 0.57 e...

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Main Authors:	Andrei A. Bardin, Tatiana G. Prokhorova, Lev I. Buravov
Format:	Article
Language:	English
Published:	MDPI AG 2023-10-01
Series:	Crystals
Subjects:	single-molecule magnet (SMM) charge ordering (CO) stripe order metal-insulator (MI) transition molecular conductors electrocrystallization
Online Access:	https://www.mdpi.com/2073-4352/13/10/1504

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author	Andrei A. Bardin Tatiana G. Prokhorova Lev I. Buravov
author_facet	Andrei A. Bardin Tatiana G. Prokhorova Lev I. Buravov
author_sort	Andrei A. Bardin
collection	DOAJ
description	A new molecular conductor, i.e., <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O), is semiconductive with substantial charge gap values (Δ<i>E</i>) of 0.57 eV (measured) and 0.37 eV (calculated). There is a full band separation despite formal average charge on BEDT-TTF of +0.5 and <i>κ</i>(kappa)-type packing of BEDT-TTF dimers that favors high conductivity. X-ray crystal structure analysis reveals complete charge ordering with full Coulomb charge on unique BEDT-TTF radical cations <b><i>A</i></b> (<i>Q<b><sub>A</sub></b></i> = +1), while unique molecules <b><i>B</i></b> are uncharged (<i>Q<b><sub>B</sub></b></i> = 0). Geometries of <b><i>A</i></b> (flat) and <b><i>B</i></b> (bent) differ considerably and are in accordance with the ascribing charges. Charge segregation is enhanced by forming tight face-to-face BEDT-TTF dimers <b><i>AA</i></b> (<i>Q<b><sub>AA</sub></b></i> = +2) and <b><i>BB</i></b> (<i>Q<b><sub>BB</sub></b></i> = 0). Strongly interacting double-charged dimers <b><i>AA</i></b> form “superstripes” running along <b><i>a</i></b> that are interleaved along <b><i>b</i></b> with chains of neutral dimers <b><i>BB</i></b>. Peculiar extremely thick (13.7 Å) four-decker insulating anion layers cast strong Coulomb potential onto the conductive layers predetermining charge localization in the latter.
first_indexed	2024-03-10T21:19:52Z
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institution	Directory Open Access Journal
issn	2073-4352
language	English
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publishDate	2023-10-01
publisher	MDPI AG
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series	Crystals
spelling	doaj.art-979af4cf455e4b7d93fe60c53e427a7d2023-11-19T16:10:11ZengMDPI AGCrystals2073-43522023-10-011310150410.3390/cryst13101504A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)Andrei A. Bardin0Tatiana G. Prokhorova1Lev I. Buravov2Center for Applied Structural Discovery, Biodesign Institute, Arizona State University, 727 East Tyler Street, Tempe, AZ 85287, USAFederal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 142432 Chernogolovka, RussiaFederal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, 142432 Chernogolovka, RussiaA new molecular conductor, i.e., <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O), is semiconductive with substantial charge gap values (Δ<i>E</i>) of 0.57 eV (measured) and 0.37 eV (calculated). There is a full band separation despite formal average charge on BEDT-TTF of +0.5 and <i>κ</i>(kappa)-type packing of BEDT-TTF dimers that favors high conductivity. X-ray crystal structure analysis reveals complete charge ordering with full Coulomb charge on unique BEDT-TTF radical cations <b><i>A</i></b> (<i>Q<b><sub>A</sub></b></i> = +1), while unique molecules <b><i>B</i></b> are uncharged (<i>Q<b><sub>B</sub></b></i> = 0). Geometries of <b><i>A</i></b> (flat) and <b><i>B</i></b> (bent) differ considerably and are in accordance with the ascribing charges. Charge segregation is enhanced by forming tight face-to-face BEDT-TTF dimers <b><i>AA</i></b> (<i>Q<b><sub>AA</sub></b></i> = +2) and <b><i>BB</i></b> (<i>Q<b><sub>BB</sub></b></i> = 0). Strongly interacting double-charged dimers <b><i>AA</i></b> form “superstripes” running along <b><i>a</i></b> that are interleaved along <b><i>b</i></b> with chains of neutral dimers <b><i>BB</i></b>. Peculiar extremely thick (13.7 Å) four-decker insulating anion layers cast strong Coulomb potential onto the conductive layers predetermining charge localization in the latter.https://www.mdpi.com/2073-4352/13/10/1504single-molecule magnet (SMM)charge ordering (CO)stripe ordermetal-insulator (MI) transitionmolecular conductorselectrocrystallization
spellingShingle	Andrei A. Bardin Tatiana G. Prokhorova Lev I. Buravov A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O) Crystals single-molecule magnet (SMM) charge ordering (CO) stripe order metal-insulator (MI) transition molecular conductors electrocrystallization
title	A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)
title_full	A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)
title_fullStr	A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)
title_full_unstemmed	A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)
title_short	A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)
title_sort	new charge ordered molecular conductor i κ i bedt ttf sub 2 sub k sup sup 18 crown 6 co sup ii sup ncs sub 4 sub ∙ h sub 2 sub o
topic	single-molecule magnet (SMM) charge ordering (CO) stripe order metal-insulator (MI) transition molecular conductors electrocrystallization
url	https://www.mdpi.com/2073-4352/13/10/1504
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A New Charge-Ordered Molecular Conductor: <i>κ</i>-(BEDT-TTF)<sub>2</sub>K<sup>+</sup>(18-crown-6)[Co<sup>II</sup>(NCS)<sub>4</sub>]∙(H<sub>2</sub>O)

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