Excited platinum atom states

Excited Platinum Atom States and their Interactions... 

All of the physical measurments point to the equivalence of all the platinum atoms (in a noninteger oxidation state) in a chain. The results of the numerous measurements on K2Pt(CN)4Bro.3(H20)s, demonstrates this system to be a one-dimensional metal undergoing a metal-insulator transition as the temperature is lowered. The far infrared and optical measurements show that the electronic excitation spectrum is not that of a simple one-dimensional metal but has a complex behavior at low frequencies. The available data from many diverse types of experiments have been analyzed in terms of numerous models. This system is currently best characterized in terms of a one-dimensional metal undergoing a Peierls transition to a semiconductor at low temperatures, with evidence for the presence of a pinned charge density wave. Further careful measurements of the partially oxidized tetracyanoplatinates are necessary to fully understand the applicability of various one-dimensional models to this class of materials. 

Much of the Pt Mossbauer work performed so far has been devoted to studies of platinum metal and alloys in regard to nuclear properties (magnetic moments and lifetimes) of the excited Mossbauer states of Pt, lattice dynamics, electron density, and internal magnetic field at the nuclei of Pt atoms placed in various magnetic hosts. The observed changes in the latter two quantities, li/ (o)P and within a series of platinum alloys are particularly informative about the conduction electron delocalization and polarization. 

Excitation to the LC states may also result in population of the CT-excited states, especially the LLCT states. These phenomena are frequently encountered in complexes containing both rc-acceptor (eg 1,10-phenantroline or 2,2 -bipyridyl) and 7r-donor ligands (eg aromatic thiols). Then the LC excitation can induce charge transfer between these ligands through central atom (LLCT) that leads to a photoredox reaction. Such reactions were reported in the case of heteroleptic organometallic compound [Rh CylLXCsHs)]3 [37], heteroleptic Re1 complex fac-[Re (L)(CO)3(bpy)]n+ [46] and metal-carbon-bonded platinum complexes [47]. 

Mossbauer Effect Spectroscopy Studies (41). Another physical probe which has been used in the characterization of platinum-iridium catalysts is Mossbauer effect spectroscopy (3,4), 52). It can be applied to catalysts in which virtually all of the metal atoms are surface atoms. In Mossbauer effect spectroscopy one is concerned with a transition between a ground state and an excited state of a nucleus (53). 

The high spin-orbit coupling constant of the platinum nucleus (x = 4,481 cm ) should facilitate both the S T intersystem crossing process and the T S radiative decay. However, the extent to which it does so in a complex will depend upon the contribution of metal atomic orbitals to the excited state. In many simple Pt(II) complexes with relatively small hgands, the metal s involvement is such that triplet state formation is very fast, of the order of 10 s [7]. Since this greatly exceeds typical singlet radiative rate constants of aromatic ligands, emissimi is then... 

The excited states of dinuclear platinum, rhodium, and iridium complexes with a variety of bridging ligands exhibit unusually diverse reactivity. These types of compound in their lowest triplet state engage in oxidative and reductive electron transfer reactions, and exciplex formation [56], They can also engage in atom transfer reactions i.e. they can abstract hydrogen atoms from a wide range of substrates as well as halogen atoms from alkyl and aryl halides. 

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