A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.

Pt-based heterobimetallic lantern complexes of the form [PtM(SOCR)(L)] have been shown previously to form intermolecular metallophilic interactions and engage in antiferromagnetic coupling between lanterns having M atoms with open shell configurations. In order to understand better the influence of the carboxylate bridge and terminal ligand on the electronic structure, as well as the metal-metal interactions within each lantern unit, a series of diamagnetic lantern complexes, [PtMg(SAc)(OH)] (1), [PtMg(tba)(OH)] (2), [PtCa(tba)(OH)] (3), [PtZn(tba)(OH)] (4), and a mononuclear control (PhP)[Pt(SAc)] (5) have been synthesized. Crystallographic data show close Pt-M contacts enforced by the lantern structure in each dinuclear case. Pt-NMR spectroscopy of 1-4, (PhP)[Pt(SAc)] (5), and several previously reported lanterns revealed a strong chemical shift dependence on the identity of the second metal (M), mild influence by the thiocarboxylate ligand (SOCR; R = CH (thioacetate, SAc), CH (thiobenzoate, tba)), and modest influence from the terminal ligand (L). Fluorescence spectroscopy has provided evidence for a Pt···Zn metallophilic interaction in [PtZn(SAc)(OH)], and computational studies demonstrate significant dative character. In all of 1-4, the short Pt-M distances suggest that metal-only Lewis donor (Pt)-Lewis acceptor (M) interactions could be present. DFT and NBO calculations, however, show that only the Zn examples have appreciable covalent character, whereas the Mg and Ca complexes are much more ionic.

Four new quasi-1D Ni-lantern chain complexes of the form [Ni(SOCR)(L)] (R = Ph, L = DABCO (1); R = Ph, L = pyz (2); R = CH, L = DABCO (3); R = CH, L = pyz (4)) were prepared from the reaction of [Ni(SOCR)(EtOH)], R = CH or Ph, with the N,N'-donor bridging ligands pyrazine (pyz) or 1,4-diazabicyclo[2.2.2]octane (DABCO). Reaction of [Ni(tba)(EtOH)], (tba = thiobenzoate) with the mono-N donor ligand quinuclidine (quin) gave the discrete Ni-lantern complex [Ni(tba)(quin)] (5), whereas reaction with pyridine led to fragmentation of the lantern and formation of the known [Ni(tba)(py)] (6). Single-crystal X-ray diffraction reveals 2-4 to be 1D chain complexes comprising DABCO or pyz ligands which bridge the Ni-lantern units. Complex 5 forms dimers through two equivalent NiS interactions. The Ni-Ni distances within the Ni-lanterns are 2.5316(18)-2.595(2) Å for the 1D chain complexes 2-4, and 2.5746(4) Å in the dimeric complex 5, respectively. Comparing the solid state magnetism of 5 to precursor [Ni(tba)(EtOH)] demonstrates a change in coupling upon change of capping ligand. Meanwhile, chains 1-4 exhibit magnetic properties consistent with an S = 1 system, due to a mixed valent system where the two Ni centers differ in spin state, while 5 possesses two S = 1 Ni(ii) centers. DFT calculations confirm low-spin S = 0 {NiS} and high-spin S = 1 {NiO} centers in each lantern. Fits to the magnetic susceptibility data of the chains suggest a weak antiferromagnetic mean field interaction is present that is largely 1-D in nature, though neither pyrazine nor DABCO promote significant magnetic interaction between neighboring Ni-lanterns.

PtVO(SOCR)4 lantern complexes and Ce(OAr)3 or Nd(OAr)3 form heterotrimetallic [Ln(OAr)3{PtVO(SOCR)4}] with linear Ln–OVPt linkages; all four exhibit slow magnetic relaxation and likely antiferromagnetic coupling.