Doping, halogens

Raman spectra have also been reported on ropes of SWCNTs doped with the alkali metals K and Rb and with the halogen Br2 [30]. It is found that the doping of CNTs with alkali metals and halogens yield Raman spectra that show spectral shifts of the modes near 1580 cm" associated with charge transfer. Upshifts in the mode frequencies are observed and are associated with the donation of electrons from the CNTs to the halogens in the case of acceptors, and downshifts are observed for electron charge transfer to the CNT from the alkali metal donors. These frequency shifts of the CNT Raman-active modes can in principle be u.sed to characterise the CNT-based intercalation compound for the amount of intercalate uptake that has occurred on the CNT wall. 

An alternative approach to stabilizing the metallic state involves p-type doping. For example, partial oxidation of neutral dithiadiazolyl radicals with iodine or bromine will remove some electrons from the half-filled level. Consistently, doping of biradical systems with halogens can lead to remarkable increases in conductivity and several iodine charge transfer salts exhibiting metallic behaviour at room temperature have been reported. However, these doped materials become semiconductors or even insulators at low temperatures. 

Semiconductor properties are imparted by doping its structure with boron, phosphorus, or arsenic atoms. Silicon is relatively inert chemically but is attacked by halogens and dilute alkalies. It has good optical transmission especially in the infra-red. 

The third member, trimethylenemethane (3), had some relevance to our studies on carbenes, since besides methylene and its simply substituted derivatives trimethylenemethane 3 is one of the few molecules having a triplet ground state.22 Also the experience with 3 could be of help in order to deal with the singlet/triplet differentiation in matrix-isolated carbenes. We learned that, if the calculated IR spectra of the singlet and triplet molecule are sufficiently different, it might be possible to determine the multiplicity of the matrix-isolated species by comparison with the experimental IR spectrum. In this context it is also worth mentioning that we were able to measure the matrix IR spectrum of 3, but a special technique (irradiation in halogen-doped xenon matrices) had to be developed in order to achieve a concentration of 3 sufficient for its IR detection.23... 

An example is trimethylenemethane (TMM), one of the first hydrocarbon biradicals whose triplet ESR spectrum was recorded (cf. Chapter 5 in this volume), but which eluded 25 years of efforts (among others by the present author) to obtain its UV-vis or IR spectrum, because the predominant product of photolysis or pyrolysis of different precursors was invariably methylenecyclopropane (MCP). Eventually, Maier et al. successfully generated a sufficient quantity of TMM, by irradiation of MCP in halogen-atom doped Xe matrices, to record the IR spectrum of this elusive compound. 

The tetrahalides 12 treated with an alkyllithium4 48 57 58 5015165 or with sodium-doped lithium metal57 undergo two sequential metal-halogen exchange and nucleophilic... 

POLYACETYLENE. A linear polymer of acetylene having alternate single and double bonds, developed in 1978. It is electrically conductive, but this property can be varied in either direction by appropriate doping either with electron acceptors (arsenic pentaflnoride or a halogen) or with electron donors (lithium, sodium). Thus, it can be made to have a wide range of conductivity from insulators to n- or >-type semiconductors to strongly conductive forms, Polyacetylene can be made in both cis and trans modifications in the form of fibers and thin films, the conductivity... 

Malleable materials can be beaten into sheets. Ductile materials can be pulled into wires. Lustrous materials have a shine. Oxides, hydrides, and halides are compounds with 0, H, and halogens respectively. Measures of intermolecular attractions other than melting point are also higher for metal oxides, hydrides, and halides than for the nonmetal compounds. A dopant is a small quantity of an intentionally added impurity. The controlled movement of electrons in doped silicon semiconductors carries digital information in computer circuitry. 

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