An in-depth correlation of the perturbation of the organic -inorganic interface topology, electronic structure, and transport properties within an extended series of 21 metallic pseudopolymorphs, β″-(BEDT-TTF)4·(guest)n ·[Re6Q6Cl8], (Q = S, Se)

André Deluzet, Roger Rousseau, Christophe Guilbaud, Isabelle Granger, Kamal Boubekeur, Patrick Batail, Enric Canadell, Pascale Auban-Senzier, Denis Jérôme

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

An in-depth analysis of a set of 21 layered structures of metallic pseudopolymorphs of general formulation, β″-(BEDT-TTF)4·(guest)n· [Re6Q6Cl8], (BEDT-TTF=bis-ethylene-dithiotetrathiafulvalene; Q = S, Se; guest = H2O, 1,4-dioxane, THF, CCl4, C2H5OH, CHCl3, CH2ClI, CH2ClBr, CH2Cl2, CH2OH-CH2OH, C5H5N, CH3COCH3, 2-hydroxy-tetrahydrofuran, CH3CN, CS2, C6H6), with diverse low-temperature behaviors, which differ solely by the nature of the cosolvent molecule selectively included during the electrocrystallization process, reveals a precise set of weak HO-H⋯Cl-μ-Re, (C-H)BEDT-TFF⋯Cl-μ-Re, C-H ⋯ Oguest, (C-H)guest ⋯ Cl-μ-Re hydrogen bonds at the organic-inorganic interface, none of which dominates any of the others and whose balance is adjusted upon substitution of one guest molecule by another. The electronic structure of the host adjusts to the weak perturbation imposed by exchanging the guest molecules and by balancing the former interfacial interactions; this correlates to a net activation of up to 0.1 eV of the energy of the HOMO level of one of the two donors, while keeping the pattern of HOMO-HOMO intermolecular interactions in the donor layer essentially unaltered. It is suggested that this controls the stability of the metallic state at low temperature or the occurrence of a metal-to-insulator phase transition for particular guests along the series. It is concluded that by allowing for numerous tiny modifications at the organic-inorganic interface within a single, robust host structure, one sees a concerted, inherently weak structural response of the system that is proportional to the magnitude of the underlying, equally weak activation of the HOMO energy of a fraction of the π-donor molecules within the slabs; this has a sizeable influence on the macroscopic transport properties of the system.

Original languageEnglish
Pages (from-to)3884-3900
Number of pages17
JournalChemistry - A European Journal
Volume8
Issue number17
DOIs
Publication statusPublished - Sep 2 2002

Fingerprint

Electron transport properties
Electronic structure
Topology
Molecules
Chemical activation
Transport properties
Hydrogen bonds
Ethylene
Substitution reactions
Phase transitions
Metals
Temperature
BEDT-TTF

Keywords

  • Cluster compounds
  • Hydrogen bonds
  • Metallic materials
  • Organic-inorganic interface
  • Radical ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

An in-depth correlation of the perturbation of the organic -inorganic interface topology, electronic structure, and transport properties within an extended series of 21 metallic pseudopolymorphs, β″-(BEDT-TTF)4·(guest)n ·[Re6Q6Cl8], (Q = S, Se). / Deluzet, André; Rousseau, Roger; Guilbaud, Christophe; Granger, Isabelle; Boubekeur, Kamal; Batail, Patrick; Canadell, Enric; Auban-Senzier, Pascale; Jérôme, Denis.

In: Chemistry - A European Journal, Vol. 8, No. 17, 02.09.2002, p. 3884-3900.

Research output: Contribution to journalArticle

Deluzet, André ; Rousseau, Roger ; Guilbaud, Christophe ; Granger, Isabelle ; Boubekeur, Kamal ; Batail, Patrick ; Canadell, Enric ; Auban-Senzier, Pascale ; Jérôme, Denis. / An in-depth correlation of the perturbation of the organic -inorganic interface topology, electronic structure, and transport properties within an extended series of 21 metallic pseudopolymorphs, β″-(BEDT-TTF)4·(guest)n ·[Re6Q6Cl8], (Q = S, Se). In: Chemistry - A European Journal. 2002 ; Vol. 8, No. 17. pp. 3884-3900.
@article{7fa1f6125dbb45e0a6dee26fa90ff0b6,
title = "An in-depth correlation of the perturbation of the organic -inorganic interface topology, electronic structure, and transport properties within an extended series of 21 metallic pseudopolymorphs, β″-(BEDT-TTF)4·(guest)n ·[Re6Q6Cl8], (Q = S, Se)",
abstract = "An in-depth analysis of a set of 21 layered structures of metallic pseudopolymorphs of general formulation, β″-(BEDT-TTF)4·(guest)n· [Re6Q6Cl8], (BEDT-TTF=bis-ethylene-dithiotetrathiafulvalene; Q = S, Se; guest = H2O, 1,4-dioxane, THF, CCl4, C2H5OH, CHCl3, CH2ClI, CH2ClBr, CH2Cl2, CH2OH-CH2OH, C5H5N, CH3COCH3, 2-hydroxy-tetrahydrofuran, CH3CN, CS2, C6H6), with diverse low-temperature behaviors, which differ solely by the nature of the cosolvent molecule selectively included during the electrocrystallization process, reveals a precise set of weak HO-H⋯Cl-μ-Re, (C-H)BEDT-TFF⋯Cl-μ-Re, C-H ⋯ Oguest, (C-H)guest ⋯ Cl-μ-Re hydrogen bonds at the organic-inorganic interface, none of which dominates any of the others and whose balance is adjusted upon substitution of one guest molecule by another. The electronic structure of the host adjusts to the weak perturbation imposed by exchanging the guest molecules and by balancing the former interfacial interactions; this correlates to a net activation of up to 0.1 eV of the energy of the HOMO level of one of the two donors, while keeping the pattern of HOMO-HOMO intermolecular interactions in the donor layer essentially unaltered. It is suggested that this controls the stability of the metallic state at low temperature or the occurrence of a metal-to-insulator phase transition for particular guests along the series. It is concluded that by allowing for numerous tiny modifications at the organic-inorganic interface within a single, robust host structure, one sees a concerted, inherently weak structural response of the system that is proportional to the magnitude of the underlying, equally weak activation of the HOMO energy of a fraction of the π-donor molecules within the slabs; this has a sizeable influence on the macroscopic transport properties of the system.",
keywords = "Cluster compounds, Hydrogen bonds, Metallic materials, Organic-inorganic interface, Radical ions",
author = "Andr{\'e} Deluzet and Roger Rousseau and Christophe Guilbaud and Isabelle Granger and Kamal Boubekeur and Patrick Batail and Enric Canadell and Pascale Auban-Senzier and Denis J{\'e}r{\^o}me",
year = "2002",
month = "9",
day = "2",
doi = "10.1002/1521-3765(20020902)8:17<3884::AID-CHEM3884>3.0.CO;2-N",
language = "English",
volume = "8",
pages = "3884--3900",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "17",

}

TY - JOUR

T1 - An in-depth correlation of the perturbation of the organic -inorganic interface topology, electronic structure, and transport properties within an extended series of 21 metallic pseudopolymorphs, β″-(BEDT-TTF)4·(guest)n ·[Re6Q6Cl8], (Q = S, Se)

AU - Deluzet, André

AU - Rousseau, Roger

AU - Guilbaud, Christophe

AU - Granger, Isabelle

AU - Boubekeur, Kamal

AU - Batail, Patrick

AU - Canadell, Enric

AU - Auban-Senzier, Pascale

AU - Jérôme, Denis

PY - 2002/9/2

Y1 - 2002/9/2

N2 - An in-depth analysis of a set of 21 layered structures of metallic pseudopolymorphs of general formulation, β″-(BEDT-TTF)4·(guest)n· [Re6Q6Cl8], (BEDT-TTF=bis-ethylene-dithiotetrathiafulvalene; Q = S, Se; guest = H2O, 1,4-dioxane, THF, CCl4, C2H5OH, CHCl3, CH2ClI, CH2ClBr, CH2Cl2, CH2OH-CH2OH, C5H5N, CH3COCH3, 2-hydroxy-tetrahydrofuran, CH3CN, CS2, C6H6), with diverse low-temperature behaviors, which differ solely by the nature of the cosolvent molecule selectively included during the electrocrystallization process, reveals a precise set of weak HO-H⋯Cl-μ-Re, (C-H)BEDT-TFF⋯Cl-μ-Re, C-H ⋯ Oguest, (C-H)guest ⋯ Cl-μ-Re hydrogen bonds at the organic-inorganic interface, none of which dominates any of the others and whose balance is adjusted upon substitution of one guest molecule by another. The electronic structure of the host adjusts to the weak perturbation imposed by exchanging the guest molecules and by balancing the former interfacial interactions; this correlates to a net activation of up to 0.1 eV of the energy of the HOMO level of one of the two donors, while keeping the pattern of HOMO-HOMO intermolecular interactions in the donor layer essentially unaltered. It is suggested that this controls the stability of the metallic state at low temperature or the occurrence of a metal-to-insulator phase transition for particular guests along the series. It is concluded that by allowing for numerous tiny modifications at the organic-inorganic interface within a single, robust host structure, one sees a concerted, inherently weak structural response of the system that is proportional to the magnitude of the underlying, equally weak activation of the HOMO energy of a fraction of the π-donor molecules within the slabs; this has a sizeable influence on the macroscopic transport properties of the system.

AB - An in-depth analysis of a set of 21 layered structures of metallic pseudopolymorphs of general formulation, β″-(BEDT-TTF)4·(guest)n· [Re6Q6Cl8], (BEDT-TTF=bis-ethylene-dithiotetrathiafulvalene; Q = S, Se; guest = H2O, 1,4-dioxane, THF, CCl4, C2H5OH, CHCl3, CH2ClI, CH2ClBr, CH2Cl2, CH2OH-CH2OH, C5H5N, CH3COCH3, 2-hydroxy-tetrahydrofuran, CH3CN, CS2, C6H6), with diverse low-temperature behaviors, which differ solely by the nature of the cosolvent molecule selectively included during the electrocrystallization process, reveals a precise set of weak HO-H⋯Cl-μ-Re, (C-H)BEDT-TFF⋯Cl-μ-Re, C-H ⋯ Oguest, (C-H)guest ⋯ Cl-μ-Re hydrogen bonds at the organic-inorganic interface, none of which dominates any of the others and whose balance is adjusted upon substitution of one guest molecule by another. The electronic structure of the host adjusts to the weak perturbation imposed by exchanging the guest molecules and by balancing the former interfacial interactions; this correlates to a net activation of up to 0.1 eV of the energy of the HOMO level of one of the two donors, while keeping the pattern of HOMO-HOMO intermolecular interactions in the donor layer essentially unaltered. It is suggested that this controls the stability of the metallic state at low temperature or the occurrence of a metal-to-insulator phase transition for particular guests along the series. It is concluded that by allowing for numerous tiny modifications at the organic-inorganic interface within a single, robust host structure, one sees a concerted, inherently weak structural response of the system that is proportional to the magnitude of the underlying, equally weak activation of the HOMO energy of a fraction of the π-donor molecules within the slabs; this has a sizeable influence on the macroscopic transport properties of the system.

KW - Cluster compounds

KW - Hydrogen bonds

KW - Metallic materials

KW - Organic-inorganic interface

KW - Radical ions

UR - http://www.scopus.com/inward/record.url?scp=0037009115&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037009115&partnerID=8YFLogxK

U2 - 10.1002/1521-3765(20020902)8:17<3884::AID-CHEM3884>3.0.CO;2-N

DO - 10.1002/1521-3765(20020902)8:17<3884::AID-CHEM3884>3.0.CO;2-N

M3 - Article

VL - 8

SP - 3884

EP - 3900

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 17

ER -