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First crystal structures of oxo-bridged [CrIIITaV] dinuclear complexes: spectroscopic, magnetic and theoretical investigations of the Cr–O–Ta core


Androš Dubraja, Lidija; Jurić, Marijana; Lafargue-Dit-Hauret, William; Pajić, Damir; Zorko, Andrej; Ozarowski, Andrew; Rocquefelte, Xavier
First crystal structures of oxo-bridged [CrIIITaV] dinuclear complexes: spectroscopic, magnetic and theoretical investigations of the Cr–O–Ta core // New journal of chemistry, 42 (2018), 13; 10912-10921 doi:10.1039/c8nj01493k (međunarodna recenzija, članak, znanstveni)


Naslov
First crystal structures of oxo-bridged [CrIIITaV] dinuclear complexes: spectroscopic, magnetic and theoretical investigations of the Cr–O–Ta core

Autori
Androš Dubraja, Lidija ; Jurić, Marijana ; Lafargue-Dit-Hauret, William ; Pajić, Damir ; Zorko, Andrej ; Ozarowski, Andrew ; Rocquefelte, Xavier

Izvornik
New journal of chemistry (1144-0546) 42 (2018), 13; 10912-10921

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Oxo-bridged complex ; chromium ; (oxalato)tantalate ; metal-to-metal charge transfer

Sažetak
Heterodinuclear complexes [Cr(bpy)2(H2O)(μ-O)Ta(C2O4)3]2·3.5H2O (1) and [H2(terpy)][Cr(terpy)(C2O4)(μ-O)Ta(C2O4)3]·0.5H2C2O4·2.5H2O (2) (bpy = 2, 2′-bipyridine ; terpy = 2, 2′:6′, 2′′-terpyridine) have been synthesised through a reaction of a tris(oxalate)oxotantalate(V) anion and a complex chromium(III) cation with corresponding aromatic N-donor ligands. These are the first examples of a Cr–O–Ta bridge in molecular compounds, and the first report of heterodinuclear complexes prepared from a tris(oxalate)oxotantalate(V) anion as a building block. Structural analysis of both compounds revealed that TaV in pentagonal bipyramid geometry is connected through a slightly bent μ-O bridge to CrIII having a distorted octahedral environment. The geometry optimization performed with density functional theory (DFT) calculations gave very good agreement with the experimentally obtained structure of 1. Room temperature solid state UV-Vis spectra were recorded for both compounds and compared to those of starting reagents, in order to test for possible new electronic transitions attributed to the metal-to-metal charge transfer between CrIII and TaV through the oxo-bridge. Infrared (IR) spectroscopy supported with DFT calculations was used to assign vibrational modes to all spectral features, especially those coming from the molecular μ-oxo bridge. Temperature dependence of magnetic properties of 1 and 2 were probed with magnetic susceptibility measurements on a SQUID magnetometer. Additionally, zero-field splitting parameters were determined from electron paramagnetic resonance (EPR) spectra of compound 1 and experimentally obtained values were confirmed by DFT calculations.

Izvorni jezik
Engleski



POVEZANOST RADA


Projekt / tema
HRZZ-IP-2014-09-4079 - Novi metal-organsi sustavi s oksalatnim i kinoidnim ligandima s podešenim svojstvima pogodnim za primjenu (Krešimir Molčanov, )
HRZZ-UIP-2014-09-8276 - Multiferični i magnetoelektrični sustavi (Damir Pajić, )

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • Arts & Humanities Citation Index (A&HCI)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus


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