Arsenic(III)-Capped 12-Tungsto-2-Arsenates(III) [M2(AsIIIW6O25)2(AsIIIOH)x]n- (M = CrIII, FeIII, ScIII, InIII, TiIV, MnII) and Their Magnetic Properties

Wenjing Liu; Jared S Kinyon; Bassem S Bassil; Zhengguo Lin; Jasleen K Bindra; Naresh S Dalal; Ulrich Kortz

doi:10.1021/acs.inorgchem.1c00965

Arsenic(III)-Capped 12-Tungsto-2-Arsenates(III) [M₂(As^IIIW₆O₂₅)₂(As^IIIOH)_x]^n- (M = Cr^III, Fe^III, Sc^III, In^III, Ti^IV, Mn^II) and Their Magnetic Properties

Inorg Chem. 2021 Jun 7;60(11):8267-8275. doi: 10.1021/acs.inorgchem.1c00965. Epub 2021 May 27.

Authors

Wenjing Liu^{1

2}, Jared S Kinyon³, Bassem S Bassil^{1

4}, Zhengguo Lin¹, Jasleen K Bindra³, Naresh S Dalal³, Ulrich Kortz¹

Affiliations

¹ Department of Life Sciences and Chemistry, Jacobs University, Campus Ring 1, 28759 Bremen, Germany.
² Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Nanjing Tech University, Nanjing 211800, China.
³ Department of Chemistry and Biochemistry, Florida State University, 95 Chiefan Way, Tallahassee, Florida 32306, United States.
⁴ Department of Chemistry, Faculty of Arts and Sciences, University of Balamand, P.O. Box 100, Tripoli, Lebanon.

PMID: 34041905
DOI: 10.1021/acs.inorgchem.1c00965

Abstract

Six arsenic(III)-capped 12-tungsto-2-arsenates(III) of the type [M₂(As^IIIW₆O₂₅)₂(As^IIIOH)_x]^n- (M = Cr^III, 1; Fe^III, 2; Sc^III, 3; In^III, 4; Ti^IV, 5; Mn^II, 6) have been synthesized in aqueous medium by direct reaction of the elements using a one-pot strategy and structurally characterized by FT-IR spectroscopy, single-crystal XRD, and elemental analysis. Polyanions 1-6 are comprised of two octahedrally coordinated guest metal ions M sandwiched between two {AsW₆} units, resulting in a structure with C_2h point-group symmetry. Polyanions 1-5 contain tri- and tetravalent metal ion guests M (M = Cr^III, Fe^III, Sc^III, In^III, and Ti^IV, respectively), and they have one {As^IIIOH} group grafted on each {AsW₆} unit, whereas the divalent Mn^II-containing derivative 6 has two such {As^IIIOH} groups grafted on each {AsW₆} unit. Magnetic studies on polyanions 3-5 over the temperature range 1.8-295 K and magnetic fields of 0-7 T confirmed that they are diamagnetic. On the other hand, polyanions 1, 2, and 6 are strongly magnetic and follow the Curie-Weiss law above 30 K. The susceptibility plots of 1 and 6 exhibit broad peaks suggesting short-range antiferromagnetic ordering, while the very weak antiferromagnetic ordering of 2 is overshadowed by traces of a paramagnetic impurity. The magnetization data of 1, 2, and 6 at 1.8 K over 0-7 T were analyzed by using the Heisenberg exchange procedure. Small (negative) values of the obtained J values help in understanding the absence of long-range antiferromagnetic ordering.