Controllable Growth of Well-Defined Regular Multiporphyrin Array Nanocrystals at the Water−Chloroform Interface

On the basis of the coordination geometry of metal ions, regular cubic, clubbed, and wirelike nanocrystals of Cd²⁺-/PtCl₆^2--mediated, and Hg²⁺-/Ag⁺-/PtCl₄^2--mediated multiporphyrin arrays have been grown at the water−chloroform interface. The nanocrystal growth process was monitored by the transmission electron microscopy (TEM), which revealed (1) an intrinsic rule for coordination polymers, that is, the geometries of metal ions (as connects for the coordination polymers) dominate the frameworks of the related polymeric nanocrystals, and (2) one kind of intuitive nanocrystal growth processes at the interfaces. Both electron diffraction and X-ray diffraction patterns indicated the formation of well-defined nanocrystals. It was found that single-/microcrystals were formed at first, and then they grew into polycrystals. The nanocrystal layer was transferred onto Si and quartz substrate surfaces by the Langmuir−Blodgett method, with its composition analyzed by X-ray photoelectron spectroscopy as well as the arrangement of porphyrin macrocycles in the nanocrystals by UV−vis absorption spectroscopy.