Stabilization of isolated mixed-valence trimers in a novel nickel dithiolene complex with CF2 substituents

被引:19
作者
Dautel, OJ [1 ]
Fourmigué, M [1 ]
机构
[1] Inst Mat Jean Rouxel, CNRS FRE 2068, Lab Sci Mol Interfaces, F-44322 Nantes 3, France
关键词
D O I
10.1021/ic0013835
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The preparation of the novel paramagnetic nickel dithiolene complex Ni(F(2)pdt)(2)(-.) (F(2)pdt(2-): 2,2-difluoro-1,3-propanediyldithioethylene. -1,2-dithiolate) and its X-ray crystal structure as n-Bu4N+ salt are described. (nBu(4)N)[Ni(F(2)pdt)(2)] (2) crystallizes in the orthorhombic system, space group Pna2(1) with a = 21.379(4) Angstrom, b = 5.9702(18) Angstrom, and c = 18.527(4) Angstrom. The radical anions are isolated from each other by the bulky n-Bu4N+ cations and exhibit a Curie-type magnetic behavior. Two reversible redox waves corresponding to the redox couples Ni(F(2)pdt)(2)(2-/-.) and Ni(F(2)pdt)(2)(-./0) are observed at -0.55 and 0.30 V vs SCE, illustrating the electron withdrawing effect of the CF2 substituents. As a consequence, (TTF)(3)(BF4)(2) oxidation of the radical anion does not afford the neutral Ni(F(2)pdt)(2)(0) but a TTF salt formulated as [TTF](3)[Ni(F(2)pdt)(2)](3)[CH2Cl2]. It crystallizes in the triclinic system, space group P (1) over bar with a = 12.330(3) Angstrom, b = 12.726(3) Angstrom, c = 15.706(3) Angstrom, a = 91.10(3), beta = 110.78(3), and gamma = 116.01(3). Donor and acceptor moieties are organized into (TTF)(3)(2+) and [Ni(F(2)pdt)(2)](3)(2-) trimers whose dicationic and dianionic charges have been inferred from the intramolecular bond lengths evolution and the singlet-tripler magnetic behavior. These trimers arrange orthogonally to each other into chess-board-like slabs, characterized by a segregation of the CF2 fragments and further stabilized by weak C-H . . .F interactions. Extended Huckel calculations show that only the nickel dithiolene complex trimer actually contributes to the magnetic susceptibility.
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页码:2083 / 2087
页数:5
相关论文
共 42 条
[1]   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
[2]  
Banks R.E., 1994, ORGANOFLUORINE CHEM
[3]  
BATAIL P, 1995, J MATER CHEM, V5, P1481
[4]   1-Deoxy-1-(4-fluorophenyl)-β-D-ribofuranose, its hemihydrate, and 1-deoxy-1-(2,4-difluorophenyl)-β-D-ribofuranose:: structural evidence for intermolecular C-H•••F-C interactions [J].
Bats, JW ;
Parsch, J ;
Engels, JW .
ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY, 2000, 56 :201-205
[5]   SYNTHESIS AND CHARACTERIZATION OF THE NICKEL AND COPPER-COMPLEXES OF THE NEW DITHIOLENE, 1,3-PROPANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE (PDDT) [J].
BEREMAN, RD ;
LU, H .
INORGANICA CHIMICA ACTA, 1993, 204 (01) :53-61
[6]   ANOMALOUS PARAMAGNETISM OF COPPER ACETATE [J].
BLEANEY, B ;
BOWERS, KD .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1952, 214 (1119) :451-465
[7]  
BROSSARD L, 1986, CR ACAD SCI II, V302, P205
[8]   CONCERNING THE BAND-STRUCTURE OF D(M(DMIT)2)2 (D=TTF,CS, NME4-M=NI,PD) MOLECULAR CONDUCTORS AND SUPERCONDUCTORS - ROLE OF THE M(DMIT)2 HOMO AND LUMO [J].
CANADELL, E ;
RAVY, S ;
POUGET, JP ;
BROSSARD, L .
SOLID STATE COMMUNICATIONS, 1990, 75 (08) :633-638
[9]   ON THE BAND ELECTRONIC-STRUCTURE OF X[M(DMIT)2]2 (X=TTF, (CH3)4N - M=NI, PD) MOLECULAR CONDUCTORS AND SUPERCONDUCTORS [J].
CANADELL, E ;
RACHIDI, IEI ;
RAVY, S ;
POUGET, JP ;
BROSSARD, L ;
LEGROS, JP .
JOURNAL DE PHYSIQUE, 1989, 50 (19) :2967-2981
[10]   MOLECULAR-METALS AND SUPERCONDUCTORS DERIVED FROM METAL-COMPLEXES OF 1,3-DITHIOL-2-THIONE-4,5-DITHIOLATE (DMIT) [J].
CASSOUX, P ;
VALADE, L ;
KOBAYASHI, H ;
KOBAYASHI, A ;
CLARK, RA ;
UNDERHILL, AE .
COORDINATION CHEMISTRY REVIEWS, 1991, 110 (01) :115-160