The paramagnetic and chiral anion [Fe(C
5O
5)
3]
3- (C
5O
52- = croconate) has been combined with the organic donorBEDT-TTF (=ET = bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor withthe first chirality-induced
phase,
-(BEDT-TTF)
5[Fe(C
5O
5)
3]·5H
2O (
1), and one of the few known paramagneticmolecular metals,
-(BEDT-TTF)
5[Fe(C
5O
5)
3]·C
6H
5CN (
2). Both compounds present layers of BEDT-TTF molecules,with the
or
packing modes, alternating with layers containing the high-spin
S = 5/2 Fe(III) anions and solventmolecules. In the
phase, the alternation of the chiral [Fe(C
5O
5)
3]
3- anions along the direction perpendicular tothe BEDT-TTF chains induces an alternation of the tilt angle of the BEDT-TTF molecules, giving rise to the observed
phase. The
phase presents a semiconductor behavior with a high room-temperature conductivity (6 S·cm
-1)and an activation energy of 116 meV. The
phase presents a metallic behavior down to ca. 120 K, where acharge localization takes place with a reentrance to the metallic state below ca. 20 K followed by a metal-semiconductor transition at ca. 10 K. The magnetic properties are dominated by the paramagnetic
S = 5/2[Fe(C
5O
5)
3]
3- anion with an extra Pauli-type paramagnetism in the metallic
phase. The ESR spectra confirm thepresence of the high-spin Fe(III)-containing anion and show a progressive localization in the organic sublatticealong with an antiferromagnetic coupling below ca. 120 K that, in the metallic
phase, could be at the origin ofthe transition from the metallic to the activated conductivity regime. The correlation between crystal structure andconductivity behavior has been studied by means of tight-binding band structure calculations which provide arationalization of the charge distribution and conductivity results.