Low-dimensional molecular solids

We report, in this work, the synthesis, physicochemical characterization, and x-ray analysis of substituted porphyrin complexes of the general type M(Por)F (M = Ga, In and Tl, Por = porphyrin), as precursors of new low-dimensional molecular solids. We also give preliminary data on their doping with iodine, and their electrical conductivity. 

Electrochemical Aspects of Low-Dimensional Molecular Solids, Michael D. Ward... 

The preparation of crystalline low-dimensional molecular solids, commonly is performed by electrocrystallization techniques wherein redox active molecules are reduced or oxidized at a working electrode in the presence of appropriate counterions. Very little is known, however, about the effect of electrochemical parameters and interfacial structure on the self assembly processes that lead to crystallization on the electrode surface. This work will describe the electrocrystallization of various crystalline molecular solids, focusing on the control of nucleation, growth, morphology and stoichiometry of these materials through manipulation of the electrochemical growth conditions and interfacial properties of the electrode. 

M.D. Ward, Electrochemical aspects of low-dimensional molecular solids, Electroanal. Chem. 16, 181 (1984). 

Rouxel J (1992) Low-dimensional solids An interface between molecular and solid-state chemistry The example of chainlike niobium and tantalum chalcogenides. Acc Chem Res 25 328-336... 

The book covers a variety of questions related to orientational mobility of polar and nonpolar molecules in condensed phases, including orientational states and phase transitions in low-dimensional lattice systems and the theory of molecular vibrations interacting both with each other and with a solid-state heat bath. Special attention is given to simple models which permit analytical solutions and provide a qualitative insight into physical phenomena. 

There are many other low-dimensional solids that have not been included here, polydiacetylene (Bloor, 1985) being one of them. Porphyrinic molecular metals show anisotropic conductivity, where the charge carriers pertain to both the metal and the ligand (Hoffman Ibers, 1983). The conductivity reaches values greater than 10 ohm cm Mn some systems and does not appear to come down to the insulator value... 

Some of the very interesting applications of these layered intercalates are in material design [3], ion exchange [4], catalysis [5], in the study of quantum-sized semiconductor particles [6], assembly of molecular multilayers at solid-liquid interfaces [7], designer electrode surfaces [8], preparation of low-dimensional conducting polymers [9], and so forth. 

---