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Abstract Organofunctionalized tetranuclear clusters [(MIICl)2(VIVO)2{((HOCH2CH2)(H)N(CH2CH2O))(HN(CH2CH2O)2)}2] (1, M=Co,2: M=Zn) containing an unprecedented oxometallacyclic {M2V2Cl2N4O8} (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single‐crystal X‐ray diffraction structure analysis. The isostructural clusters are formed of edge‐sharing octahedral {VO5N} and trigonal bipyramidal {MO3NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of1and2in an unusual two‐mode fashion, unobserved previously. In the crystalline state, the clusters of1and2are joined by hydrogen bonds to form a three‐dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [Jiso(VIV−VIV)=−5.4(1); −3.9(2) cm−1], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [Jiso(VIV−CoII)=−12.6 and −7.5 cm−1] contained in1.
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IR spectroscopic characterization of 3d transition metal carbene cations, FeCH 2 + and CoCH 2 + : periodic trends and a challenge for DFT approaches
A combination of IR multiple-photon dissociation (IRMPD) action spectroscopy and quantum chemical calculations was employed to investigate the [M,C,2H]+(M = Fe and Co) species.
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- Award ID(s):
- 2313553
- PAR ID:
- 10575127
- Publisher / Repository:
- Royal Society
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 26
- Issue:
- 13
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 9948 to 9962
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d4cp00026a
