(EDT-TTF-CONH2)6[Re6Se8(CN)6], a metallic Kagome-type organic-inorganic hybrid compound:: Electronic instability, molecular motion, and charge localization

被引:77
作者
Baudron, SA
Batail, P
Coulon, C
Clérac, R
Canadell, E
Laukhin, V
Melzi, R
Wzietek, P
Jerome, D
Auban-Senzier, P
Ravy, S
机构
[1] Univ Angers, CNRS, UMR 6200, Lab Chim Ingn Mol & Mat Angers, F-49045 Angers, France
[2] CNRS, Ctr Rech Paul Pascal, UPR 8641, Ctr Rech Paul Pascal, F-33600 Pessac, France
[3] CSIC, Inst Ciencia Mat Barcelona, ICMAB, E-08193 Barcelona, Spain
[4] ICREA, Barcelona 08010, Spain
[5] Univ Paris 11, CNRS, UMR 8502, Phys Solides Lab, F-91405 Orsay, France
关键词
D O I
10.1021/ja0523385
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(EDT-TTF-CONH2)(6)[Re6Se8(CN)(6)], space group M, was prepared by electrocrystallization from the primary amide-functionalized ethylenedithiotetrathiafulvalene, EDT-TTF-CONH2 (E-1/2(1) = 0.49 V vs SCE in CH3CN), and the molecular cluster tetraanion, [Re6Se8(CN)(6)](4-) (E-1/2 = 0.33 V vs SCE in CH3CN), equipped with hydrogen bond donor and hydrogen bond acceptor functionalities, respectively. Its Kagome topology is unprecedented for any TTF-based materials. The metallic state observed at room temperature has a strong two-dimensional character, in coherence with the Kagome lattice symmetry, and the presence of minute amounts of [Re6Se8(CN)(6)]((3-)center dot) identified by electron spin spectroscopy. A structural instability toward a distorted form of the Kagome topology of lesser symmetry is observed at ca. 180 K. The low-temperature structure is associated with a localized, electrically insulating electronic ground state and its magnetic susceptibility accounted for by a model of uniform chains of localized S = 1/2 spins in agreement with the 100 K triclinic crystal structure and band structure calculations. A sliding motion, within one out of the three (EDT-TTF-CONH2)(2) dimers coupled to the [Re6Se8(CN6)((3-)center dot)]/[Re6Se8(CN6)(4-)] proportion at any temperature, and the electronic ground state of the organic-inorganic hybrid material are analyzed on the basis of ESR, dc conductivity, H-1 spin-lattice relaxation, and static susceptibility data which qualify a Mott localization in [EDT-TTF-CONH2](6)[Re6Se8(CN)(6)]. The coupling between the metal-insulator transition and a structural transition allows for the lifting of a degeneracy due to the ternary axis in the high temperature, strongly correlated metallic phase which, in turn, leads to Heisenberg chains at low temperature.
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页码:11785 / 11797
页数:13
相关论文
共 64 条
[1]  
Abragam A., 2002, PRINCIPLES NUCL MAGN
[2]   COUNTERINTUITIVE ORBITAL MIXING IN SEMI-EMPIRICAL AND ABINITIO MOLECULAR-ORBITAL CALCULATIONS [J].
AMMETER, JH ;
BURGI, HB ;
THIBEAULT, JC ;
HOFFMANN, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (12) :3686-3692
[3]  
[Anonymous], 1998, PRINCIPLES CONDENSED
[4]   Kagome lattice - A molecular toolkit for magnetism [J].
Atwood, JL .
NATURE MATERIALS, 2002, 1 (02) :91-92
[5]   VARIABLE MAGNETIC-INTERACTIONS IN AN ORGANIC RADICAL SYSTEM OF (M-N-METHYLPYRIDINIUM ALPHA-NITRONYL NITROXIDE).X- - A POSSIBLE KAGOME ANTIFERROMAGNET [J].
AWAGA, K ;
OKUNO, T ;
YAMAGUCHI, A ;
HASEGAWA, M ;
INABE, T ;
MARUYAMA, Y ;
WADA, N .
PHYSICAL REVIEW B, 1994, 49 (06) :3975-3981
[6]   FERROMAGNETIC AND ANTIFERROMAGNETIC INTERMOLECULAR INTERACTIONS IN THE 2-DIMENSIONAL TRIANGULAR LATTICE OF THE M-N-METHYLPYRIDINIUM NITRONYL NITROXIDE CATION RADICAL [J].
AWAGA, K ;
INABE, T ;
MARUYAMA, Y ;
NAKAMURA, T ;
MATSUMOTO, M .
CHEMICAL PHYSICS LETTERS, 1992, 195 (01) :21-24
[7]   Introduction: Molecular conductors [J].
Batail, P .
CHEMICAL REVIEWS, 2004, 104 (11) :4887-4890
[8]   Electrocrystallization, an invaluable tool for the construction of ordered, electroactive molecular solids [J].
Batail, P ;
Boubekeur, K ;
Fourmigue, M ;
Gabriel, JCP .
CHEMISTRY OF MATERIALS, 1998, 10 (10) :3005-3015
[9]   Singular crystalline β′-Layered topologies directed by ribbons of self-complementary amide ••• amide ring motifs in [EDT-TTF-(CONH2)2]2X (X = HSO4-, ClO4-, ReO4-, AsF6-):: Coupled activation of ribbon curvature, electron interactions, and magnetic susceptibility [J].
Baudron, SA ;
Avarvari, N ;
Batail, P ;
Coulon, C ;
Clérac, R ;
Canadell, E ;
Auban-Senzier, P .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (38) :11583-11590
[10]   Jahn-Teller distortion of the open-shell 23-electron chalcogenide rhenium cluster cores in crystals of the series, {[Re6Q8]3+(X-)6}3- (Q = S, Se; X = Cl, CN) [J].
Baudron, SA ;
Deluzet, A ;
Boubekeur, K ;
Batail, P .
CHEMICAL COMMUNICATIONS, 2002, (18) :2124-2125