Coordinated and clathrated guests in the (3)(infinity)[Hg6As4](4+) bicompartmental framework: Synthesis, crystal and electronic structure, and properties of the novel supramolecular complexes [Hg6As4](CrBr6)Br and [Hg6As4](FeBr6)Hg-0.6
2003 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 9, no 14, 3201-3208 p.Article in journal (Refereed) Published
Two new supramolecular complexes [Hg6As4](CrBr6)Br (1) and [Hg6As4](FeBr6)Hg-0.6 (2) have been prepared by the standard ampoule technique and their crystal structures determined. Both crystallize in the cubic space group PO with the unit cell parameter a = 12.275(1) (1) and 12.332(1) Angstrom (2), and Z = 4. Their structures consist of bicompartmental, three-dimensional [Hg6As4](4+) frameworks with cavities of two different sizes occupied by guest anions of different type. ne bigger cavities are filled with the octahedral MBr6n- ions (M = Cr or Fe; n = 3 or 4), whereas the smaller cavities trap either Br- ions (1) or Hg-0 (2). The analysis of the host-guest contacts has allowed a classification of the octahedral guests as coordinated and the monatomic guests as clathrated. Magnetic measurements and ESR spectroscopy data have given information about the interaction between the host and guests. Band structure calculations (HF and hybrid DFT level) indicate that both 1 and 2 are non-metallic, with a band gap of approximately 1.5 eV (B3LYP), and that the interaction between the host and guests is of predominantly electrostatic character. It is shown that though the electrostatic host-guest interaction is weak it plays an important role in assembling the perfectly ordered supramolecular architectures.
Place, publisher, year, edition, pages
2003. Vol. 9, no 14, 3201-3208 p.
arsenic, band structure, host-guest systems, mercury, solid-state structures, supramolecular chemistry
IdentifiersURN: urn:nbn:se:kth:diva-5075DOI: 10.1002/chem.200204687ISI: 000184479300003OAI: oai:DiVA.org:kth-5075DiVA: diva2:7780
QC 201009062005-04-262005-04-262010-09-06Bibliographically approved