Synthesis, Crystal Structures, and Magnetic Properties of One-Dimensional Mixed Cyanide- and Phenolate-Bridged Heterotrimetallic Complexes

Abstract

Two one-dimensional (1D) cyanide- and phenolate-bridged heterotrimetallic complexes {[CuIIMnII(L1)][FeIII(bpb)(CN)2]} n ·(ClO4) n ·(H2O) n (1) and {[CuIIMnII(L1)][CrIII(bpb)(CN)2]} n ·(ClO4) n ·(H2O) n (2) (bpb2− = 1,2-Bis(pyridine-2-carboxamido)benzenate) have been designed and prepared based on cyanide-containing building blocks K[M(bpb)(CN)2] [M = Fe(III) and Cr(III)] together with compartmental macrocyclic Schiff-base complex [CuMn(L1)]·(ClO4)2, in which H2L1 is derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior of these two complexes. These results seem to represent the first example of 1D infinite cyanide- and phenolate-bridged single chain-like compounds containing three kinds of spin carriers 3d-3d′-3d′′prepared by a stepwise method.

Structure and Magnetic Properties of an Original {CuIIMnIIWV} Heterotrimetallic Coordination Polymer

“…The geometrical parameters concerning the {Cu II Mn II L} fragment are in agreement with similar reported examples. [7b] The close inspection of the packing diagram reveals hydrogen bonds connecting the double chains as shown in Figures S4 and S5.…”

“…For analogous bis‐phenoxido‐bridged Cu II ‐Mn II binuclear complex, [Cu II Mn II L 2 ] 2+ (Scheme ), the metal ions are held together by a dissymmetric compartmental Robson‐type ligand . Both binuclear systems are characterized by an S = 2 ground state, which results from a significant antiferromagnetic interaction between S = 1/2 Cu II and S = 5/2 Mn II centers, and are thus good building‐block candidates for designing heterotrimetallic magnetic complexes and networks.…”

“…Both binuclear systems are characterized by an S = 2 ground state, which results from a significant antiferromagnetic interaction between S = 1/2 Cu II and S = 5/2 Mn II centers, and are thus good building‐block candidates for designing heterotrimetallic magnetic complexes and networks. For example, the self‐assembly of [Cu II Mn II L 1 ] 2+ and [Cr III (ampy)(CN) 4 ] – modules (ampy = aminomethylpyridine) results in a 2‐D 3d‐3d'‐3d'' network which possess a ferrimagnetic state below 4.3 K.[6b] So far, only three heterotrimetallic chains, [Cu II Mn II L 2 M III ] n (M = Fe, Cr)[7a] and [Cu II Mn II L 2 W V ] n ,[7b] have been reported and obtained starting from [Cu II Mn II L 2 ] 2+ and heteroleptic cyanido metalloligands.…”

Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties

“…When the dinitrogenous base quinoxaline, is employed, the resulting polymer is no longer linear as a result of the asymmetrical intramolecular and interchain forces. When the β-diketonate is acac − a zigzag chain structure is observed for trans-[Co(acac) 2 (qox)] n [19]; however, when the β-diketonate is DBM − , a wavelike chain structure is observed for trans-[Co(DBM) 2 Some of the tert-butyl groups in 3 and 4 show a two-fold disorder. The tert-butyl groups are designated by the numbers of the central carbon atoms (see Figures 4 and 6).…”

“…The structures of the wavelike polymers were determined by single-crystal X-ray diffraction and the wave characteristics analysed using the sine trigonometric function. Wavelike characteristics of some coordination polymers have been noted previously [1][2][3][4][5][6][7][8][9][10][11][12]; however, we have been unable to find any references where trigonometric functions were used to analyze the structural data. Recently, a review article has been published on one-dimensional coordination polymers [13].…”