Use of a rhenium cyanide nanomagnet as a building block for new clusters and extended networks

Abstract

Derivatives of the single molecule magnet (SMM) {[Re(triphos)(CN)(3)](4)[MnCl](4)} (Re(4)Mn(4)) {[Re(triphos)(CN)(3)](4)[Mn(CH(3)CN)](4)}(ClO(4))(4) (2) and {[Re(triphos)(CN)(3)](4)[Mn(ClO(4))](3)[Mn(CH(3)OH)(CH(3)O)]} (3), were prepared by reacting [Et(4)N][Re(triphos)(CN)(3)] (1) with Mn(ClO(4))(2)·6H(2)O. Reaction of sodium dicyanamide, NaN(CN)(2), with compound 2 in CH(2)Cl(2) results in the product {[Re(triphos)(CN)(3)](4)[Mn(N(CN)(2))](4)} (4), in which each Mn(II) site is terminated by a dicyanamide ligand. A similar reaction of compound 3 in CH(2)Cl(2)-MeOH solution with LiTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) leads to the formation of {[Re(triphos)(CN)(3)](4)[Mn(TCNQ-TCNQ)(3)(Mn(HTCNQ)(CH(3)O))]} (5) whose structure is best described as a chain of dimers of Re(4)Mn(4) cubes bridged by sigma-bonded (TCNQ(2))(2-) linkers with one capping HTCNQ ligand.

Molecular magnetic materials based on 4d and 5d transition metals

“…Interestingly, the SMM behavior of the {Mn II 4 Re II 4 } cluster is retained in the 1-D chain. 84 Finally, the mer-[Ru III (CN-sap)(CN) 3 ] 2À (S = 1 2 ) precursor was recently reported by Gao and Lau et al, in which a Ru III center is located in a distorted octahedral geometry with three cyanide ligands in a meridional arrangement. 85 Reaction of this building unit with Mn II or Co II ions afforded two isostructural 1-D ladder compounds M II (MeOH) 3 -[Ru III (CN-sap)(CN) 3 ]Á2MeOH (M = Mn II , Co II ) (Fig.…”

Synthesis of Manganese ZIF-8 from [Mn(BH4)2·3THF]·NaBH4

“…In this work, we tried to synthesize Mn-based ZIF-8 architecture. Only five compounds having a nondistorted tetrahedral Mn 2+ -4N geometry have been reported according to the Cambridge Crystallographic Data Centre database, and it is a challenge to construct an open framework. − We first attempted to synthesize Mn-ZIF-8 from a conventional solvothermal reaction. When we utilized Mn­(NO 3 ) 2 ·6H 2 O or Mn­(CH 3 COO) 2 ·4H 2 O as a precursor, Mn 3 O 4 was the main product because of the thermal decomposition of manganese salts (Figure S3).…”

Single-molecule magnet engineering: building-block approaches

“…Other fac-tricyanido building blocks such as [Re II (triphos)(CN) 3 ] À (triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane) have been studied by Dunbar and co-workers who have reported a {Mn II 4 Re II 4 } 189,190 and polymeric systems 191 based on this module. The structure of the parent complex, 31, is a molecular cube as depicted in Fig.…”

“…As the local spins are all S = 1/2, the magnetic anisotropy is likely the result of the orbital angular momentum of the low-spin Fe III modules. A structural analogue is obtained when [TpFe III (CN) 3 ] À is reacted with [Ni II 189,190 and polymeric systems 191 based on this module. The structure of the parent complex, 31, is a molecular cube as depicted in Fig.…”