Quasi-1D chains of PT-containing heterobimetallic lantern complexes and resultant properties
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Abstract
The series of compounds {[Na(15C5)][PtM(SAc)4(NCS)] (M = Co, 1; Ni, 2; Zn, 3) or {[Na(12C4)2][PtM(SAc)4(NCS)] (M = Co, 4; Ni, 5; Zn, 6; Mn, 7) was prepared and thoroughly characterized. Compounds 1-3 are discrete molecules in the solid state, while 4-7 crystallize as ion-separated species. In contrast to monomeric 1-7, [PtCr(tba)4(NCS)]∞ (8) forms a quasi-1D coordination polymer comprising {PtCr}+ lantern units and (NCS)- ligands connected in a zig-zag fashion. Solid state magnetic characterization of 8 reveals intra-chain ferromagnetic coupling between Cr(III) centers of J/kB = 1.7(4) K.
The series {[PtM(SAc)4(pyz)](pyz)}∞ (M = Co, 11; Ni, 12) and {[PtM(SAc)4]2(DABCO)}∞ (M = Co, 13; Ni, 14; Zn, 15) were also prepared. In the solid state 11 and 12 form linear chains with an unbound equivalent of pyrazine spacing the chains apart, while 13-15 form chains in which two lanterns bridged by one ligand are connected by Pt…Pt interactions between units. Initial studies reveal 11 displays slow magnetic relaxation in the solid state, while 13 and 14 show antiferromagnetic coupling through the Pt…Pt interactions (J = -10 cm-1 for 13, -32 cm-1 for 14).
Two rare examples of lantern complexes featuring the vanadyl ion were prepared, [Pt(V=O)(SAc)4] (19) and [Pt(V=O)(tba)4] (20). Compound 19 crystallizes as a dimer with a close Pt…Pt interaction, while 20 forms a dimer with inter-lantern Pt…S interactions. Solid state magnetic characterization for 19 displays antiferromagnetic coupling (J = -2.35 cm-1) through intermolecular nearest neighbor interactions.
A new monothiocarbamate backbone ligand was used to prepare {PtM(SOCpip)4(py)} (M = Co, 21; Ni, 22; Zn, 23; Mn, 24). The monothiocarbamate ligand donates more electron density into the lantern core than monothiocarboxylates. Compound 24 is the first crystallographically characterized {PtMn} lantern.
Two derivatives of Magnus’ Green Salt, Millon’s salt {[Cu(NH3)4][PtCl4]}∞ (25) and its Br analogue {[Cu(NH3)4][PtBr4]}∞ (26) were prepared and structurally characterized. The two crystallize as linear, quasi-1D chains with a repeating, alternating, Pt…Cu interaction, and both contain inter- and intra-chain hydrogen bonding.
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Attribution-NoDerivatives 4.0 International