Extended Linear Chain Compounds: Volume 1

Linear chain substances span a large cross section of contemporary chemistry ranging from covalent polymers, to organic charge transfer com­ plexes to nonstoichiometric transition metal coordination complexes. Their commonality, which coalesced intense interest in the theoretical and exper­ imental solid state physics/chemistry communities, was based on the obser­ vation that these inorganic and organic polymeric substrates exhibit striking metal-like electrical and optical properties. Exploitation and extension of these systems has led to the systematic study of both the chemistry and physics of highly and poorly conducting linear chain substances. To gain a salient understanding of these complex materials rich in anomalous aniso­ tropic electrical, optical, magnetic, and mechanical properties, the conver­ gence of diverse skills and talents was required. The constructive blending of traditionally segregated disciplines such as synthetic and physical organic, inorganic, and polymer chemistry, crystallography, and theoretical and ex­ perimental solid state physics has led to the timely development of a truly interdisciplinary science. This is evidenced in the contributions of this monograph series. Within the theme of Extended Linear Chain Compounds, experts in important, but varied, facets of the discipline have reflected upon the progress that has been made and have cogently summarized their field of specialty. Consequently, up-to-date reviews of numerous and varied aspects of "extended linear chain compounds" have developed. Within these vol­ umes, numerous incisive contributions covering all aspects of the diverse linear chain substances have been summarized.

1. The Solution Properties of One-Dimensional Metal Chain Complexes.- 1. Introduction.- 2. Association of Square d8 Metal Complexes.- 2.1. Rhodium(I) Isocyanide Complexes; Self-Association.- 2.2. Iridium(I) Isocyanide Complexes; Self-Association.- 2.3. Chugaev’s Red Salt, (CH3NC)2Pt(C4H9N4)+X?; Self-Association.- 2.4. Pt(CN)24; Self-Association.- 2.5. [(RNC)4Pt][Pt(CN)4]; Ion Pairs.- 3. Mixed Valence Chain Compounds.- 3.1. Halide-Bridged Chains.- 3.2. Metal-Metal-Bonded Chains.- 3.3. Some Comments on the Mechanism of Formation of Mixed Valence Chain Compounds.- Notation.- References.- 2. Mass Spectrometry of Low-Dimensional Materials.- 1. Introduction.- 2. Instrumentation.- 2.1. Sample Introduction.- 2.2. Types of Ionization.- 2.3. Ion Separation.- 3. Mass Spectrometry Combinations.- 3.1. Pyrolysis Mass Spectrometry.- 3.2. Thermal Analysis Mass Spectrometry.- 3.3. Stress Mass Spectrometry.- 4. Mass Spectrometric Applications of Low-Dimensional Materials.- 4.1. Poly(sulfurnitride), polythiazyl, (SN)X.- 4.2. Polyacetylene.- 4.3. Graphite.- 5. Conclusion.- References.- 3. The Synthesis, Structure, Electrical Conduction Properties, and Theory of Divalent, Tetravalent, and One-Dimensional Partially Oxidized Tetracyanoplatinate Complexes.- 1. Introduction.- 2. Divalent Tetracyanoplatinates.- 2.1. Structural Studies.- 2.2. Optical Studies.- 2.3. Electrical Conduction Studies.- 3. Tetravalent Tetracyanoplatinates.- 3.1. Structural Studies.- 3.2. Solution, Optical, and Electrical Conduction Studies.- 4. Partially Oxidized Tetracyanoplatinate (POTCP) Metals.- 4.1. The Synthesis of POTCP Metals.- 4.2. The Molecular Structure of POTCP Metals.- 4.3. Anion-Deficient POTCP Salts.- 4.4. Cation-Deficient POTCP Salts.- 4.5. X-Ray Diffuse Scattering at Room Temperature and the Degree of Partial Oxidation.- 4.6. The Temperature Dependence of X-Ray Diffuse Scattering and Elastic Neutron Scattering.- 4.7. Inelastic Neutron Scattering, Infrared and Raman Spectroscopy.- 5. Summary and Discussion.- Notation.- References.- 4. Linear Chain Bis(oxalato)platinate Salts.- 1. Introduction.- 2. Survey of Reported Bis(oxalato)platinate Salts.- 3. Solution Chemistry of Bis(oxalato)platinate Salts.- 4. Degree of Partial Oxidation and the Peierls Superstructure.- 5. Structural Studies.- 5.1. Bis(oxalato)platinate(II) Salts.- 5.2. Partially Oxidized Bis(oxalato)platinate Salts.- 5.3. Non-Peierls Superstructures in Partially Oxidized Bis(oxalato)-platinate Salts.- 5.4. Intermodular Backbonding between Oxalate Ligands.- 6. Solid State Properties.- 6.1. Integral Oxidation State Salts.- 6.2. Partially Oxidized Salts.- 7. Comparison of the Properties of Partially Oxidized Bis(oxalato)platinate and Tetracyanoplatinate Salts.- 7.1. Type of Compound.- 7.2. Properties in Solution.- 7.3. Structural Features.- 7.4. Non-Peierls Superstructures.- 8. Conclusions.- Notation.- References.- 5. A Comprehensive Review of Linear Chain Iridium Complexes.- 1. Introduction.- 2. Halotricarbonyliridium Complexes: Ir(CO)3X, X=Cl, Br, or I.- 2.1. Syntheses and Physical Properties.- 2.2. X-Ray Structural Results.- 2.3. Analytical Results.- 2.4. Band Calculations.- 2.5. Mass Spectra.- 2.6. X-Ray Diffuse Scattering.- 2.7. Polarized Reflectance Spectra.- 2.8. Summary.- 3. Dihalodicarbonyliridate Complexes.- 3.1. Synthesis and Reactivity.- 3.2. Characterization and Physical Properties.- 3.3. Summary.- Notation.- References.- 6. Highly Conductive Halogenated Low-Dimensional Materials.- 1. Introduction.- 1.1. Strategies for Synthesizing Highly Conductive Low-Dimensional Materials.- 1.2. General Properties of Halogens Relevant to the Synthesis of Conducting Materials.- 2. Techniques for the Characterization of Halogens in Conductive Materials.- 2.1. Resonance Raman and Infrared Spectroscopy.- 2.2. Mössbauer Spectroscopy.- 2.3. Diffraction Techniques.- 2.4. Extended X-Ray Absorption Fine Structure (EXAFS).- 2.5. Optical Spectroscopy.- 2.6. Nuclear Quadrupole Resonance Spectroscopy.- 2.7. X-Ray Photoelectron Spectroscopy.- 3. General Synthetic Methodology.- 4. Stacked Organic Systems.- 4.1. Polycyclic Aromatic Hydrocarbons.- 4.2. Organonitrogen Systems.- 4.3. Organochalcogenide Systems.- 5. Stacked Metal-Organic Systems.- 5.1. Glyoximates and Related Materials.- 5.2. ?-Electron Tetraazaannulenes 271.- 5.3. ?-Electron Metallomacrocycles 278.- 5.4. Other Tetraazaannulenes.- 5.5. Thiolato Complexes.- 6. Stacked Inorganic Systems.- 7. Polymers.- 7.1. Organochalcogenide Systems.- 7.2. Poly(sulfurnitride), (SN)x.- 7.3. Polyacetylene.- 7.4. Face-to-Face Polymetallomacrocycles.- 8. Graphite.- 9. Conclusions and Prospects.- References.- 7. Structural Aspects of Iodine-Containing Low-Dimensional Materials.- 1. Introduction.- 2. Survey of Structures, Iodine Species, and Lattice Repeats.- 3. Relation between Stoichiometry and Structure: Prediction of Unknown Structures.- 4. Disorder in the Iodine Lattice.- 4.1. Types of Disorder in Columnar Structures and Their Manifestation in the X-Ray Pattern.- 4.2. Degrees of Disorder in N(CH3)3H(TCNQ)I.- 5. Iodine-Channel Wall Interactions.- 6. Comments on the Relative Stability of Various Iodine Species.- 7. Concluding Remarks.- Notation.- References.- 8. Linear Chain Platinum Haloamines.- 1. Introduction.- 2. Platinum(II) Compounds.- 2.1. Tetraammine- and Tetraammineplatinum(II) Chains [Pt(NH3)4]2+ and [PtL4]2+ Ions.- 2.2. Triamminehaloplatinum(II) Salts, [PtL3X]+Y?.- 2.3. Diamminedihaloplatinum(II), PtL2X2, Compounds.- 2.4. Aminetrihaloplatinates(II), [PtX3L]?Ions.- 2.5. Tetrahaloplatinates(II), [PtX4]2? Ions.- 3. Pt(II)-Pt(IV) Haloamine Mixed-Valence Materials.- 3.1. Chains of Dications [PtL4]2+[PtL4X2]2+ (Wolffram’s Salt Analogs).- 3.2. Chains of Monocations.- 3.3. Neutral Chains.- 3.4. Chains of Anions.- 3.5. Chains of Dianions.- 3.6. Comparison of Pt-X Pt Distances along the Different Chains.- 4. Conclusions.- Notation.- References.- 9. Optical Properties of Linear Chain Haloamine Platinum Complexes.- 1. Introduction.- 1.1. Types of Linear Chain Haloamine Complexes.- 1.2. Optical Spectra of Molecular and Ionic Species.- 2. Magnus-Type Compounds.- 2.1. Variations in Metal-Metal Spacings.- 2.2. Crystal Spectra of Magnus-Type Salts.- 3. Molecular Crystals.- 3.1. (Ethylenediamine)dichloroplatinum(II), Pt(en)Cl2.- 3.2. (Ethylenediamine)dibromoplatinum(II), Pt(en)Br2.- 3.3. Cis- and Trans-diamminedichloroplatinum(II).- 3.4. (Ethylenediamine)dichloropalladium(II), Pd(en)Cl2.- 4. Mixed-Valence Crystals.- 4.1. Molecular Crystals.- 4.2. Ionic Mixed-Valence Compounds.- 4.3. Octahedral PtIV Defect Inclusions in PtII Compounds.- 4.4. Nature of the Mixed-Valence Transition.- 4.5. Partially Oxidized Magnus’ Salt.- 5. Summary.- 5.1. Comparison of Haloamine Platinum and Palladium Systems.- 5.2. Contrasts between the Haloamine Platinum Systems and the One-Dimensional Conductors.- Notation.- References.