PtVO(SOCR)4 lantern complexes and Ce(OAr)3 or Nd(OAr)3 form heterotrimetallic [Ln(OAr)3{PtVO(SOCR)4}] with linear Ln–OVPt linkages; all four exhibit slow magnetic relaxation and likely antiferromagnetic coupling.
Metallophilic interactions, weak
interactions between closed-shell
metal atoms, have been recently utilized to create unique nanostructures
with anisotropy of electronic properties along the direction of the
interaction. The strength of the metallophilic interaction is an important
factor for the design of these nanostructures. Recently, Doerrer and
co-workers presented a general metathesis route to create extended
chains of metallophilic double salts with two modular opposite-charge
ions with Au(I) and Pt(II) centers without bridging ligands. Here,
we apply theoretical and experimental angle-resolved Raman spectroscopy
to identify the vibrational signature associated with the Au(I)–Pt(II)
interaction in the double salt wire, [Pt(terpy)Cl][Au(CN)2)]. Our study reveals six Raman-active low-energy phonon modes below
75 cm–1 that are anisotropic, as shown by their
polarization dependence. By analysis of the low-energy Raman spectrum
and the nature of the associated phonon modes, we identify one mode
to be associated with the intrachain Pt–Au interactions with
a frequency of 57 cm–1. We show that the polarization
dependence of the Raman spectrum is the key to elucidating directional
metallophilic modes.
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