Platinum Stacking Interactions in Homoleptic Platinum Polymers

Abstract

Recent breakthroughs in low‐dimensional nanostructures have led to a renewal of interest in polymers composed of platinum complexes. The surge of research into one‐dimensional platinum complexes in the 1970s and 1980s has given way to a steady progression of investigations that have explored new ligands, characterization techniques and applications. The ongoing synthesis and characterization of new tetra(cyano)platinate, bis(oxalato)platinate and other homoleptic platinum complexes has allowed examination of the influence of organic and inorganic cations on the Pt–Pt distance and the importance of small molecules in stabilizing the stacking interactions. In particular, complexes of [Pt(C≡NR)4]2+ and [PtI(bipy)2]+ show potential to display short stacking interactions. This microreview focuses on the progress in the synthesis and characterization of homoleptic complexes with short Pt–Pt distances and avenues for the development of new classes of complexes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Interactions of weakly coordinating anions with tripalladium sandwich complexes

“…In addition the triflate containing complexes can alternate between an isolated, tri-substituted complex and a linear, bis-substituted, neutral polymer. This ability to form one-dimensional coordination polymers also suggests the potential for the formation of higher-dimensional structures analogous to known systems containing palladium and platinum polymers [16].…”

“…For some time our group has been interested in the unique properties of organometallic systems with closely interacting metal centres [15,16]. More recently our group has been interested in the formation of new complexes based upon the tripalladium ditropylium core [Pd 3 Tr 2 ] 2þ discovered by Murahashi and coworkers and expanded upon by our group [17e21].…”

Synthesis and Crystal Structure of the Partially Oxidized Cyanoplatinates Rb1.75[Pt(CN)4]·1.25H2O and Cs1.75[Pt(CN)4]·0.5H2O

“…The anisotropic physical properties of partially oxidized tetracyanoplatinates have attracted great interest because of their one‐dimensional metallic character and their relatively high electronic conductivity. In the latest review on this class of complexes1 the potential of polymers with short Pt–Pt distances for the development of sensors and further promising technological applications has been highlighted. The prototype, K 2 [Pt(CN) 4 ]Br 0.33 · 3H 2 O has been extensively studied and well characterized by the pioneer of the field, Krogmann ,2 and in subsequent studies performed by Zeller 3.…”

Luminescent Benzoquinolate‐Isocyanide Platinum(II) Complexes: Effect of Pt⋅⋅⋅Pt and π⋅⋅⋅π Interactions on their Photophysical Properties

“…It is well known that square-planar Pt II complexes show a remarkable tendency to self-assemble into one-dimensional (1D) architectures directed by Pt II ···Pt II interactions. [1] Typical are the double complex salts (DCS) consisting of infinite alternating stacks of cations and anions with the platinum atoms aligned linearly and separated by approximately [3] or [PtA C H T U N G T R E N N U N G (CNR) 4 ]A C H T U N G T R E N N U N G [PtCl 4 ], [4] and the wellknown DCS [PtA C H T U N G T R E N N U N G (CNR) 4 ][Pt(CN) 4 ]. [4][5] In these cases stacking is largely controlled by electrostatic interactions, but a small contribution from covalent Pt···Pt bonding interactions is also present.…”