An adaptable heterometallic trinuclear coordination cluster in the synthesis of tailored one-dimensional architecture: Structural characterization, magnetic analysis and theoretical calculations. (14th December 2015)

• Record Type: Journal Article
• Authors: Ghosh, Soumavo; Giri, Sanjib; Ghosh, Ashutosh
• Is Part Of: Polyhedron. Volume 102(2015)
• Page Start: 366
• Page End: 374
• Publication Date: 2015-12-14
• Subjects: Crystal engineering -- Heterometallic -- Building block -- Magnetic exchange -- Density functional theory; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.10.014
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: The adaptability of [(CuL α-Me )2 Co] 2+ tecton towards carboxylate coligands has been exploited in the synthesis of rationally designed discrete trinuclear and 1D heterometallic architectures having similar magnetic properties which are supported by DFT. Abstract: A new trinuclear complex [(CuL α-Me )2 Co(bnz)2 ] (1 ) has been synthesized by using a metalloligand [CuL α-Me ] (H2 L α-Me = N, N′-bis(α-methylsalicylidene)-1, 3-propanediamine, bnz = benzoate) with trans -coordinated syn – syn bridging benzoate group (1 κO :2 κO ′). The syn – syn coordinative selectivity of carboxylate towards this trinuclear unit leads exclusively to the formation of linear coordination cluster. Such coordinative adaptability is exploited for supramolecular assembly using a dicarboxylate linker, terephthalate (tph, 1, 4-benzenedicarboxylate) which yielded a tailored one-dimensional quasi-linear coordination polymer [(CuL α-Me )2 Co(tph)] n ·2 n H2 O (2 ) having the linear trinuclear node. Isothermal magnetization measurement at 2 K suggests that both1 and2 posses S = 1/2 ground spin state indicating the presence of antiferromagnetic coupling at low temperature. The variable-temperature magnetic susceptibility measurements also reveal that both compounds are antiferromagnetically coupled with exchange coupling constants ( J ) of −17.3 and −9.2 cm −1 for1 and2, respectively. The nature and magnitude of exchange interactions are further corroborated by density functional calculations.