Polyoxomolybdenum(V/VI)-sulfite compounds: Synthesis, structural, and physical studies
Φόρτωση...
Ημερομηνία
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
American Chemical Society
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Inorg Chem
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
Reaction of (Na2MoO4)-O-VI center dot 2H(2)O with (NH4)(2)SO3 in the mixed-solvent system H2O/CH3CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH4)(4)[(Mo4SO16)-S-VI]center dot H2O (1), while the same reaction in acidic aqueous solution (pH = 5) yielded (NH4)(4)[(Mo5S2O21)-S-VI]center dot 3H(2)O (2). Compound {(H(2)bipy)(2)[(Mo5S2O21)-S-VI]center dot H2O}(x) (3) was obtained from the reaction of aqueous acidic solution of (Na2MoO4)-O-VI center dot 2H(2)O with (NH4)(2)SO3 (pH = 2.5) and 4,4'-bipyridine (4,4'-bipy). The mixed metal/sulfite species (NH4)(7)[Co-III((Mo2O4)-O-V)(NH3)(SO3)(6)]center dot 4H(2)O (4) was synthesized by reacting (Na2MoO4)-O-VI center dot 2H(2)O with CoCl2 center dot 6H(2)O and (NH4)(2)SO3 with precise control of pH (5.3) through a redox reaction. The X-ray crystal structures of compounds 1, 2, and 4 were determined. The structure of compound 1 consists of a ring of four alternately face- and edge-sharing (MoO6)-O-VI octahedra capped by the trigonal pyramidal sulfite anion, while at the base of the Mo-4 ring is an oxo group which is asymmetrically shared by all four molybdenum atoms. Compound 3 is based on the Strandberg-type heteropolyion [(Mo5S2O21)-S-VI](4-), and these coordinatively saturated clusters are joined by diprotonated 4,4'-H(2)bipy(2+) through strong hydrogen bonds. Compound 3 crystallizes in the chiral space group C2. The structure of compound 4 consists of a novel trinuclear [(CoMo2SO32-)-Mo-III-S-V] cluster. The chiral compound 3 exhibits nonlinear optical (NLO) and photoluminescence properties. The assignment of the sulfite bands in the IR spectrum of 4 has been carried out by density functional calculations. The cobalt in 4 is a d(6) octahedral low-spin metal atom as it was evidenced by magnetic susceptibility measurements, cw EPR, BVS, and DFT calculations. The IR and solid-state UV-vis spectra as well as the thermogravimetric analyses of compounds 1-4 are also reported.
Περιγραφή
Λέξεις-κλειδιά
bond-valence parameters, potential basis-sets, polarization functions, crystal-structure, transition-elements, sulfite, anion, polyoxomolybdate, complexes, clusters
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
<Go to ISI>://000248011300028
http://pubs.acs.org/doi/pdfplus/10.1021/ic700460b
http://pubs.acs.org/doi/pdfplus/10.1021/ic700460b
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας