Self‐Assembly of Cluster‐Based Nanoscopic Supramolecules into One‐Dimensional Coordination Polymers

Abstract

Octahedral metal clusters[Nb6Cl12(CN)6]4−,(Mn(Salen))+(or(Mn(7-MeSalen))+) (Salen=N,N′-ethylene-bis-(salicylidene)iminate) and ditopic organic linkers (4,4′-bpe(trans-1, 2-bis(4-pyridyl)-ethylene) or4,4′-dpyo(4,4′-dipyridylN,N′-dioxide)) self-assemble to form three cluster-based 1D coordination polymers:[Mn(Salen)(MeOH)2]2{(4,4′-dpyo)[(Mn(Salen))2(Nb6Cl12(CN)6)]}·2MeOH(1),{(4,4′-bpe)[(Mn(7-MeSalen))2(Mn(7-MeSalen)(H2O))2(Nb6Cl12(CN)6)]}·1.5MeCN·8H2O(2), and[(4,4′-bpe)(Mn(Salen)(H2O))2]{(4,4′-bpe)2[(Mn(Salen)(MeOH))2(Mn(Salen))2(Nb6Cl12(CN)6)][(Mn(Salen))2(Nb6Cl12(CN)6)]}·16H2O(3). Single crystal X-ray diffraction analyses show that the frameworks of the three coordination polymers are built of heterotrimeric and/or heteropentameric supramolecular species linked by ditopic organic ligands. The framework of1consists of anionic chains built of heterotrimeric dianions[(Mn(Salen))2(Nb6Cl12(CN)6)]2−(T) linked by4,4′-dpyo. The chains run along two directions ([0 2 −2] and [0 3 3]) leading to the formation of channels along the crystallographic (a) direction where the cations [Mn(Salen)(S)2]+and solvent molecules are located. Also,2was reported earlier, it possesses a neutral 1D chain built of neutral heterpentameric supramolecules:[(Mn(7‐MeSalen))2(Mn(7‐MeSalen)(S))2(Nb6Cl12(CN)6)](P) linked by4,4′-bpeligands. Hydrogen bonds between non-bridging cyanide ligands and coordinated solvent molecules connect the chains into 2D hydrogen-bonded frameworks. Finally,3features an anionic chain, built of alternating heterotrimers[(Mn(Salen))2(Nb6Cl12(CN)6)]2−and heteropentamers[(Mn(Salen)(S))2(Mn(Salen))2(Nb6Cl12(CN)6)]linked by the organic spacer4,4′-bpe. The anionic charge is compensated by the in situe-assembled[Mn(Salen)(S)(4,4′‐bpe)Mn(Salen)(S)]2+dimers. Magnetic measurements reveal that the Mn(III) ions are well isolated and only weak magnetic interactions are observed. The thermal stability of the three compounds was investigated.

Supramolecular Chains and Coordination Nanowires Constructed of High-Spin CoII9WV6 Clusters and 4,4′-bpdo Linkers

“…The octahedral [Re 6 E 8 ­(CN) 6 ] 4– (E = S, Se) clusters formed the porous Prussian Blue like 3D networks, whereas trigonal bypiramidal {[M A II ­(L 1 ) 2 ] 3 ­[M B III ­(CN) 6 ] 2 } (L 1 = chelate) clusters and starlike heptanuclear {[Mn III ­(L 2 )] 6 ­[M III ­(CN) 6 ]} 3+ (L 2 = salen type ligands; M = Cr, Fe, Co) cations were connected into coordination chains. The series of 1.7–2.4 nm sized clusters {[M 6 Cl 12 ­(CN) 6 ]­[Mn­(salen)] n } ( n −4) (M = Nb, Ta; n = 1–4, 6) were joined through a series of ditopic organic linkers into coordination polymers. , Taking interest in high-spin clusters, we connected for the first time {Mn II ­[Mn II ­(MeOH) 3 ] 8 ­[W V ­(CN) 8 ] 6 } Mn 9 W 6 clusters (∼1.8 nm in diameter) by 4,4-bpy (4,4′-bpy = bipyridine) and dpe (dpe = trans -1,2-di­(4-pyridyl)­ethylene) linkers into 2D and 3D networks, respectively. The resulting {Mn II 9 ­[W V ­(CN) 8 ] 6 ­(dpe) 5 ­(MeOH) 10 }·14MeOH revealed the unique structure, where nanosized cyanido-bridged wires were joined by dpe ligands into an antiferromagnetic ( T N = 3.5 K) network with 3D I 1 O 2 dimensionality topology …”

“…The series of 1.7−2.4 nm sized clusters {[M 6 Cl 12 (CN) 6 ][Mn-(salen)] n } (n−4) (M = Nb, Ta; n = 1−4, 6) were joined through a series of ditopic organic linkers into coordination polymers. 34,35 Taking interest in high-spin clusters, we connected for the first time {Mn II [Mn II (MeOH) 3 ] 8 [W V -(CN) 8 ] 6 } Mn 9 W 6 clusters (∼1.8 nm in diameter) 36 by 4,4bpy (4,4′-bpy = bipyridine) 37 and dpe (dpe = trans-1,2-di(4pyridyl)ethylene) 38 linkers into 2D and 3D networks, respectively. The resulting {Mn II 9 [W V (CN nanosized cyanido-bridged wires were joined by dpe ligands into an antiferromagnetic (T N = 3.5 K) network with 3D I 1 O 2 dimensionality topology.…”