Depending on the stoichiometric ratio, squaric acid (3,4-dihydroxy -3-cyclobutene-1,2-dione, H(2)SQA) reacts with [(eta(6)-C6H6)(2)Cr] in THF to form the crystalline material [(eta(6)-C6H6)(2)Cr]-[HSQA] (1) and in water to yield [{(eta(6)-C6H6)(2)Cr}(2)][SQA] . 6 H2O (3); it also reacts with [(eta(5)-C5H5)(2)Co][OH] in water to form [{(eta(5)-C5H5)(2)Co}(2)][SQA] . 6 H2O (4). Compound 1 is almost isostructural with the previously reported salt [(eta(5)-C5H5)(2)Co][HSQA] (2); its structure is based on pi-pi stacks between the benzene ligands and the hydrogen squarate anionic chains (pi-pi distance 3.375 Angstrom). Compounds 3 and 4 are isomorphous and have a structure in which layers organometallic cations intercalate with layers of water molecules hydrogen bonded to squarate dianions. All crystals contain charge-assisted C-H delta(+)... O delta(-) hydrogen bonds between the organometallic and the organic components, while negative O-H(-)... O(-) and O-H ... O(2-1) interactions are present in the pairs 1/3 and 2/4, respectively. In constrast to most organic salts of [(eta(5)-C6H6)(2)Cr](+) and [(eta(5)-C5H5)(2)Co](+) which are yellow, crystals of compounds 1-4 are orange. Reflectance spectra measured on the crystalline material I show the presence of an intense tail that can be assigned to a charge-transfer transition through the [(eta(6)-C6H6)(2)Cr](+)/ [HSQA] pi-stacking interactions, while the pi stacking in 2 causes only a broadening of the band. The magnetic behaviour of 1 and 3 has been investigated by SQUID magnetometry. Both compounds are characterised by a weak antiferromagnetic interaction between the S=1/2 Cr centres of the [(eta(6)-C6H6)(2)Cr](+) cations, which is significantly stronger in 1 due to the pi-stacking with the HSQA(-) anions.
Anions Derived from Squaric Acids Form Interionic p-Stack and Layered Hydrogen Bonded Superstructures with Organometallics Sandwich Cations. The Magnetic Behavior in the p-Stacked System [mu6-(C6H6)2Cr][H2C2O4] / D. BRAGA; L. MAINI; F. GREPIONI; A. CANESCHI; R. SESSOLI; L. PRODI. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 6:(2000), pp. 1310-1317. [10.1002/(SICI)1521-3765(20000417)6:8<1310::AID-CHEM1310>3.3.CO;2-K]
Anions Derived from Squaric Acids Form Interionic p-Stack and Layered Hydrogen Bonded Superstructures with Organometallics Sandwich Cations. The Magnetic Behavior in the p-Stacked System [mu6-(C6H6)2Cr][H2C2O4]
CANESCHI, ANDREA;SESSOLI, ROBERTA;
2000
Abstract
Depending on the stoichiometric ratio, squaric acid (3,4-dihydroxy -3-cyclobutene-1,2-dione, H(2)SQA) reacts with [(eta(6)-C6H6)(2)Cr] in THF to form the crystalline material [(eta(6)-C6H6)(2)Cr]-[HSQA] (1) and in water to yield [{(eta(6)-C6H6)(2)Cr}(2)][SQA] . 6 H2O (3); it also reacts with [(eta(5)-C5H5)(2)Co][OH] in water to form [{(eta(5)-C5H5)(2)Co}(2)][SQA] . 6 H2O (4). Compound 1 is almost isostructural with the previously reported salt [(eta(5)-C5H5)(2)Co][HSQA] (2); its structure is based on pi-pi stacks between the benzene ligands and the hydrogen squarate anionic chains (pi-pi distance 3.375 Angstrom). Compounds 3 and 4 are isomorphous and have a structure in which layers organometallic cations intercalate with layers of water molecules hydrogen bonded to squarate dianions. All crystals contain charge-assisted C-H delta(+)... O delta(-) hydrogen bonds between the organometallic and the organic components, while negative O-H(-)... O(-) and O-H ... O(2-1) interactions are present in the pairs 1/3 and 2/4, respectively. In constrast to most organic salts of [(eta(5)-C6H6)(2)Cr](+) and [(eta(5)-C5H5)(2)Co](+) which are yellow, crystals of compounds 1-4 are orange. Reflectance spectra measured on the crystalline material I show the presence of an intense tail that can be assigned to a charge-transfer transition through the [(eta(6)-C6H6)(2)Cr](+)/ [HSQA] pi-stacking interactions, while the pi stacking in 2 causes only a broadening of the band. The magnetic behaviour of 1 and 3 has been investigated by SQUID magnetometry. Both compounds are characterised by a weak antiferromagnetic interaction between the S=1/2 Cr centres of the [(eta(6)-C6H6)(2)Cr](+) cations, which is significantly stronger in 1 due to the pi-stacking with the HSQA(-) anions.File | Dimensione | Formato | |
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