The use of molecular clusters as a basis of molecular single-electronic systems is considered experimentally and theoretically. The Langmuir-Blodgett formation and scanning tunneling microscope study of structures with chemically different cluster molecules is described. I-V curves and control curves of molecular single-electron transistors based on various single molecules were studied at room temperature. Comparison of experimental I-V curves with simulated ones allows us to identify a regime of slow energy relaxation of electrons in experimental transistors. Experimental study of electron transport through the planar molecular nanosystems has shown a correlated character of electron tunneling in such systems.