Integration of Trinuclear Triangle Copper(II) Secondary Building Units in Octacyanidometallates(IV)-Based Frameworks

Olaf Stefanczyk; Kunal Kumar; TingYun Pai; Guanping Li; Shin-Ichi Ohkoshi

doi:10.1021/acs.inorgchem.2c01294

Integration of Trinuclear Triangle Copper(II) Secondary Building Units in Octacyanidometallates(IV)-Based Frameworks

Inorg Chem. 2022 Jun 13;61(23):8930-8939. doi: 10.1021/acs.inorgchem.2c01294. Epub 2022 Jun 2.

Authors

Olaf Stefanczyk¹, Kunal Kumar¹, TingYun Pai¹, Guanping Li¹, Shin-Ichi Ohkoshi¹

Affiliation

¹ Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

PMID: 35652381
DOI: 10.1021/acs.inorgchem.2c01294

Abstract

The design and synthesis of high-dimensional materials based on secondary building blocks (SBUs) play a pivotal role in the further development of functional molecular materials. Herein, the self-assembly of Cu(II) ions, pyrazole (Hpz), and octacyanidometallate(IV) anions in the presence of water produced two new isostructural three-dimensional systems {[Cu₃(μ₃-OH)(μ-pz)₃(H₂O)₃]₂[M(CN)₈]}·nH₂O (M = W, 1, and Mo, 2). 1 and 2 consist of trinuclear triangle copper(II) (TTC) SBUs and octacyanidometallates(IV). At room temperature, both assemblies display strong antiferromagnetic interactions within the TTC entities with an average Cu^II···Cu^II isotropic magnetic coupling constant of about -145 cm^-1. Moreover, a detailed analysis of magnetic data revealed the presence of spin frustration with antisymmetric magnetic exchange-coupling constants of around +32 and +46 cm^-1 for 1 and 2, respectively. Finally, quantum chemical calculations explained their magnetic and optical properties.