Linear Chain Bis(oxalato)platinate Salts

Underhill, Allan E.; Watkins, David M.; Williams, Jack M.; Carneiro, K.

doi:10.1007/978-1-4613-3249-7_4

Cited by 14 publications

(8 citation statements)

References 38 publications

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“…Found short intermetallic separations in Tl(I)-cyanoximates are due to the “metallophilic” interactions that lately were increasingly often found in coinage metal and platinum complexes . The latter are known for their 1D electrical conductivity. − , …”

Section: Resultsmentioning

confidence: 99%

“…Coordination polymers with unusual structures and properties have attracted considerable attention due to their interesting topologies and fascinating potential applications in (a) molecular electronics, and (b) as photo- and magnetic materials. − The main focus in development and studies of coordination polymers was on transition metals, while less attention was given to main group metals, despite their well-established importance in electro- and conventional luminescence, fluorescent sensors, and photovoltaic applications. ,− Thus, in the area of molecular electronics search for one-dimensional (1D) conductive solids, attention was mainly on mixed valence transition metals homometallic complexes and especially platinum . Two major types of electric conductors originated from work with the latter metal: MX, KCP, and partially oxidized cyano-platinates (POCP) types of 1D solids.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Studies of Coordination-Polymeres With Isomeric Pyridylcyanoximes: Route to Metal Ribbons With Very Short Tl···Tl Separations

Marcano

Gerasimchuk

Nemykin

et al. 2012

Crystal Growth & Design

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Two isomeric pyridylcyanoximes, H(3PCO) and H(4PCO), containing nitrogen atoms of the heterocycle at 3-and 4-positions, respectively, were synthesized and thoroughly characterized using IR (including 15 N labeling), UV−visible, 1 H, 13 C one-and two-dimensional NMR spectroscopy, and X-ray analysis. The H(3PCO) exists as a mixture of syn-and anti-isomers in solutions, contrary to H(4PCO) which is present only as an antiisomer. Both compounds have planar geometry in the solid state and form elegant zigzag chains via H-bonding between the oxime group and the N-atom of the heterocycle. The H(3PCO) and H(4PCO) upon addition of a base form colored conjugated and solvatochromic anions in solutions. The reaction of the hot aqueous solution of Tl 2 CO 3 with solid isomeric pyridylcyanoximes leads to TlL, which were characterized by elemental analyses, IR spectroscopy, and X-ray analysis. Both complexes represent three-dimensional coordination polymers of different complexities where cyanoxime anions act as bridging ligands. Thallium(I) atoms in Tl(3PCO) and Tl(4PCO) form infinite, planar "metal ribbons" with unusually short intermetallic distances: 3.705 Å in Tl(3PCO) and 3.635 Å in Tl(4PCO) respectively, which are close to that in metallic thallium (3.465 Å). The latter compound has the second shortest Tl•••Tl thallophillic interaction reported in the literature thus far. Both yellow Tl(3PCO) and orange Tl(4PCO) are insulators at ambient conditions: R ∼ 1 × 10 11 Ohm.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Studies of Coordination-Polymeres With Isomeric Pyridylcyanoximes: Route to Metal Ribbons With Very Short Tl···Tl Separations

Marcano

Gerasimchuk

Nemykin

et al. 2012

Crystal Growth & Design

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“…There are a large number of nonstoichiometric halogenated compounds such as (TTF)X x and (metal phthalocyanine)I x , which have been compiled in the review of Marks and Kalina . KCP (K 2 [Pt(CN) 4 ]Br 0.3 ·3H 2 O) and the related platinum complexes are also within this category, but they are not dealt with in this review. A number of nonstoichiometric charge-transfer compounds have been reported on the basis of chemical analysis.…”

Section: Introductionmentioning

confidence: 99%

Organic Conductors with Unusual Band Fillings

Mori

2004

Chem. Rev.

124

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“…The enhanced electrical conduction of 1 is due to increased intermetallic orbital overlaps. The conduction band of 1D Pt complexes such as KCP is generally composed of 5d z 2 orbitals of Pt ions, 4a, and application of pressure causes enhancement of intermetallic orbital overlaps of 5d z 2 . It has been reported that the compression along the platinum chain direction is largest for Pt II glyoximato complexes, [Pt(dpg) 2 ], [Pt(dmg) 2 ], and [Pt(bqd) 2 ] (dpg = diphenylglyoximato, dmg = dimethylglyoximato, and bqd = 1,2-benzoquinonegyloximato), and consequently, the electrical conductivities at room temperature are drastically increased with increasing pressure.…”

Section: Resultsmentioning

confidence: 99%

Electrical Conducting Bis(Oxalato)platinate Complex with Direct Connection of Cu^II Ions

et al. 2006

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Reactions of K1.62[Pt(ox)2].2H2O and [Cu(bpy)(H2O)3](NO3)2 yielded partially oxidized one-dimensional (1D) bis(oxalato)platinates of [Cu(bpy)(H2O)n]6[Pt(ox)2]7.7H2O (n = 2, 3, or 4) (1) and [Cu(bpy)(H2O)n]8[Pt(ox)2]10.8H2O (n = 3 or 4) (2). The average oxidation numbers of the platinum ions in 1 and 2 are +2.29 and +2.40, respectively. Complexes 1 and 2 crystallize in the triclinic P and monoclinic C2/c space groups, respectively, and the [Pt(ox)2]n- anions are stacked along the crystallographic b axis with 7-fold periodicity for 1 and 10-fold periodicity for 2. In 1, an oxalato ligand in the platinum chain directly coordinates to a paramagnetic [Cu(bpy)(H2O)3]2+ ion, whereas no such direct coordination was observed for 2. The electrical conductivity of 2 at room temperature along the platinum chain is approximately 3 orders of magnitude smaller (sigma||= 1.3 x 10(-3) S cm(-1)) than that of 1 (sigma|| = 0.9-0.5 S cm(-1)), and the activation energies of 1 and 2 are 29 and 67 meV, respectively. The longest inter-platinum distances in 1 and 2 are 2.762 and 3.0082 A, respectively, and this is responsible for the lower electrical conductivity of 2. An X-ray oscillation photograph taken along the b axis of 1 reveals the 7-fold periodicity in the 1D chain, consistent with the period of the Peierls distortion estimated from the degree of partial oxidation. The semiconducting state of 1 can therefore be regarded as a commensurate Peierls state. The magnetoresistance of 1 at ambient pressure indicates no interaction between conduction electrons in the platinum chain and local spins of the paramagnetic CuII ions. Application of hydrostatic pressures of up to 3 GPa enhances electrical conduction, as is often seen as the usual pressure effect on the electrical conductivity, which is due to enhanced orbital (Pt-5dz2) overlap by pressure application.

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Linear Chain Bis(oxalato)platinate Salts

Cited by 14 publications

References 38 publications

Synthesis, Characterization, and Studies of Coordination-Polymeres With Isomeric Pyridylcyanoximes: Route to Metal Ribbons With Very Short Tl···Tl Separations

Synthesis, Characterization, and Studies of Coordination-Polymeres With Isomeric Pyridylcyanoximes: Route to Metal Ribbons With Very Short Tl···Tl Separations

Organic Conductors with Unusual Band Fillings

Electrical Conducting Bis(Oxalato)platinate Complex with Direct Connection of Cu^II Ions

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Linear Chain Bis(oxalato)platinate Salts

Cited by 14 publications

References 38 publications

Synthesis, Characterization, and Studies of Coordination-Polymeres With Isomeric Pyridylcyanoximes: Route to Metal Ribbons With Very Short Tl···Tl Separations

Synthesis, Characterization, and Studies of Coordination-Polymeres With Isomeric Pyridylcyanoximes: Route to Metal Ribbons With Very Short Tl···Tl Separations

Organic Conductors with Unusual Band Fillings

Electrical Conducting Bis(Oxalato)platinate Complex with Direct Connection of CuII Ions

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Product

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Electrical Conducting Bis(Oxalato)platinate Complex with Direct Connection of Cu^II Ions