Octanuclearity and tetradecanuclearity in manganese chemistry: an octanuclear manganese(ii)/(iii) complex featuring the novel [Mn8(µ4- O)2(µ3-OH)2]14+ core and [Mn10IIMn4IIIO4(O2CMe)20{(2-py)2C(OH)O}4] (2-py = 2-pyridyl)

Abstract

Reactions of Mn sources with di-2-pyridyl ketone, (2-py)2CO, and phenyl 2-pyridyl ketone oxime, (ph)(2-py)CNOH, give the novel clusters [Mn10(II)Mn4(III)O4(O2CMe)20[(2-py)2C(OH)O]4] 1 and [Mn4(II)Mn4(III)O2(OH)2(O2CPh)10[(ph)(2-py)CNO]4] 2, respectively, which possess low-spin ground states; the observed tetradecanuclearity in 1 is extremely rare in 3d-metal chemistry, while the core of 2 has a unique topology consisting of two linked [Mn2(II)Mn2(III)O(OH)] units.

Phenyl 2‐Pyridyl Ketone and Its Oxime in Manganese Carboxylate Chemistry: Synthesis, Characterisation, X‐ray Studies and Magnetic Properties of Mononuclear, Trinuclear and Octanuclear Complexes

“…These reaction schemes have led [9] to a variety of Fe, Co, Ni, Cu, Zn clusters with nuclearities ranging from three to twelve and with interesting magnetic properties, including SMM behaviour. [9j] In Mn carboxylate chemistry the most impressive cluster isolated [10] is [Mn 10 II Mn 4 III O 4 (O 2 CMe) 20 {(2-py) 2 C(OH)O} 4 ]; the observed tetradecanuclearity is extremely rare in 3d-metal chemistry. Recently we have extended our efforts to ligands (Figure 1) that present a structural similarity to (2-py) 2 CO; our goals are to investigate to what extent the use of such ligands might affect the identity of the obtained products compared with (2-py) 2 CO and to what extent this might thus prove to be a route to new cluster types.…”

“…A small portion of this work has been communicated previously. [10] There is currently a renewed interest in the coordination chemistry of oximes.…”

Aquated divalent zinc, cobalt and cadmium complexes of 2-pyridinyl-4-pyridinylmethanone and assembly of their hydrogen-bonded networks

“…3). 3 The eight-coordinate Cd1 atom is surrounded by four L ligands (ligation modes (b) and (c) in Scheme 1), each acting in the chelating mode, leading to a distorted dodecahedral coordination environment at the cadmium center. The six-coordinate Cd2 atom is surrounded by the 4-pyridyl N atoms of a pair of trans-related tridentate L ligands and four aqua ligands to form an octahedral coordination sphere, thus acting as a node that links adjacent dodecahedral CdL 4 moieties into a stairs-like infinite chain ( Fig.…”

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The reaction of 2-pyridinyl-4-pyridinylmethanone with Zn(II), Co(II) and Cd(II) salts gives rise to different linear coordination polymers each linked into a three-dimensional network by intermolecular hydrogen-bonding between the aqua ligands, with additional p-p stacking interactions in the case of the Co(II) and Cd(II) complexes.Functioning as a ligand, di-2-pyridinylmethanone (di-2-pyridyl ketone) can exist in its neat keto form, doubly and singly deprotonated gem-diol forms, and as the monoanion of its hemiacetal form [1][2][3][4][5]. The synthetic and structural chemistry of polynuclear metal complexes stabilized by various forms of di-2-pyridinylmethanone has attracted much interest in the past decade, especially in the designed construction of polynuclear complexes as single-molecule magnets [1].

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“…Functioning as a ligand, di-2-pyridinylmethanone (di-2-pyridyl ketone) can exist in its neat keto form, doubly and singly deprotonated gem-diol forms, and as the monoanion of its hemiacetal form [1][2][3][4][5]. The synthetic and structural chemistry of polynuclear metal complexes stabilized by various forms of di-2-pyridinylmethanone has attracted much interest in the past decade, especially in the designed construction of polynuclear complexes as single-molecule magnets [1].…”