A paramagnetic quasi-1D chain comprised of Pt/Rh possessing an unpaired electron

Abstract

In this manuscript we review the structure of the novel 1-D chain complex, {[PtRh(PVM) 2 (NH 3 ) 2 Cl 2.5 ] 2 [Pt 2 (PVM) 2 (NH 3 ) 4 ] 2 (PF 6 ) 6 Á 2MeOH Á 2H 2 O} n (4) (PVM ¼ pivalamidate), consisting of mixed-valence dimeric complexes with appreciably extended metal-metal bondings. Compound 4 is made up of octameric segments, each of which consists of two platinum-rhodium dinuclear complexes and a tetrameric platinum unit. The charge of 19+ for the Pt 6 Rh 2 octameric segment in 4 was deduced from the number of the independent PF 6 À counter ions, and is the supporting evidence for one unpaired electron per one octameric segment. The tetrameric platinum unit in 4 is the structural motif that is observed in [Pt 2 (PVM) 2 (NH 3 ) 4 ](PF 6 ) 2 Á H 2 O (2) and [Pt 4 (PVM) 4 (NH 3 ) 8 ](PF 6 ) 4 (ClO 4 ) Á 2H 2 O (3 ¼ ''platinum blue'' with one electron delocalized over the four platinum atoms). On the basis of the EPR, magnetic susceptibility, and electrical conductivity results, the nature of the unpaired electron in 4 is discussed. r

Remarkable Structural Diversity of N-Pyrrolidine-cyanoxime and its Ni(II) Complexes

“…This interaction is so pronounced and strong that it dictates the inclusion of the nonpolar solvent molecule between two molecules of the cyanoxime (SI 18) and is manifested in short distances between N and Cl atoms when drawn at their van der Waals radii (SI 19). This type of closed-shell interaction was previously observed between O and S, Se, and Te in “chalcogen bonding”, between heavy main group elements Br and I in the “halogen bonding”, and between heavy transition metals in homometallic assemblies Cu---Cu, Ag---Ag, Au---Au, and Pt---Pt, and in heterometallic arrays such as Tl---Pt and Tl---Pb, Tl---Rh . These intermetallic short contacts belong to a new, and so far, poorly characterized and understood metallophilic interactions .…”

“…This type of closed-shell interaction was previously observed between O and S, Se, and Te in "chalcogen bonding", 58 between heavy main group elements Br and I in the "halogen bonding", 59 and between heavy transition metals in homometallic assemblies Cu---Cu, Ag---Ag, Au---Au, and Pt---Pt, and in heterometallic arrays such as Tl---Pt and Tl---Pb, 60 Tl---Rh. 61 These intermetallic short contacts belong to a new, and so far, poorly characterized and understood metallophilic interactions. 62 An observation in the current work of similar closedshell contacts between N and Cl atoms is a rare find.…”

Electrical conductive coordination polymers

“…Its solid-state structure revealed a [Pt 6 Rh 2 ] 19+ repeating octameric core bridged by twocoordinated chloride ions rendering a [-Pt-Rh-Pt 4 -Rh-Pt-Cl-] n infinite chain. 92,94 The octamer can be viewed as being formed by four dimeric units: two inner Pt-Pt dimers (Pt1-Pt2 and Pt3-Pt4) and two outer Pt-Rh dimers (Pt5-Rh1 and Pt6-Rh2), all of them doubly bridged by pivalamidate ligands that warrant both close metal-metal contacts and interdimeric hydrogen bond formation between amide oxygen and amine groups along the chain. Since two ammonia groups complete the coordination requirements of the Pt cations, two monodentate chloride ligands complete the Rh1 and Rh2 environments and balance the charge.…”

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

“…In contrast to the synthetic methods for these finite chains, crystals of an infinite one-dimensional (1-D) chain are generally obtained by the oxidation of d8 square-planar metals connecting to other metals at the d z 2 orbital, resulting in partially oxidized d z 2 bands showing metallic chains. , Infinite 1-D chains with metal–metal bonds, such as K 2 [Pt­(CN) 4 ]­Br 0.3 ·3H 2 O (KCP) and Magnus’ green salt, extend from end-to-end in the crystal and have been treated as target compounds with solid physical properties. , In a similar manner to the appearance of HMSCs, in infinite 1-D chains, several heterometallic chains in which different kinds of metal are regularly aligned with metal–metal bonds have been synthesized; − the construction methodologies were: the HOMO–LUMO interaction at the d z 2 orbital (σ-type) orbitals between two kinds of complex were discovered . The significant feature for these heterometallic 1-D chains is the modulation of their electronic structures; in the chains composed of a single kind of metal, σ-type orbitals become HOMO (valence band), but in heterometallic chains, a π-type , and a δ-type − ,, orbitals can be either HOMO or a singly occupied molecular orbital. Therefore, not only for their conductivity but also for their magnetism, heterometallic 1-D chains are expected to be candidates for magnetic molecular conductors …”