This review is dedicated to various functional nanoarchitectonic nanocomposites based on molecular octahedral metal atom clusters (Nb₆, Mo₆, Ta₆, W₆, Re₆). Powder and film nanocomposites with two-dimensional, one-dimensional and zero-dimensional morphologies are presented, as well as film matrices from organic polymers to inorganic layered oxides. The high potential and synergetic effects of these nanocomposites for biotechnology applications, photovoltaic, solar control, catalytic, photonic and sensor applications are demonstrated. This review also provides a basic level of understanding how nanocomposites are characterized and processed using different techniques and methods. The main objective of this review would be to provide guiding significance for the design of new high-performance nanocomposites based on transition metal atom clusters. GRAPHICAL ABSTRACT

First fabrication of a Ta₆-based nanocomposite coating, for energy saving applications, by an EPD solution process.

This review paper summarizes our very recent works on the synthesis of multifunctional transparent nanocomposite thin films or coatings based on metal atom clusters by an electrophoretic deposition (EPD) process. Eight different octahedral atom clusters with niobium, molybdenum or tantalum as metallic cores were used to prepare highly transparent thin films in the visible. Green, yellow, orange, red and brown colored films were successfully fabricated by coating on a transparent conductive oxide glass substrate. Transparent nanocomposite films with prominent luminescent properties were obtained by using Mo₆ clusters whereas ultra-violet (UV) and near infrared (NIR) filters were realized by using Nb₆ or Ta₆ clusters. The EPD process appears to be a new strategy to fabricate highly transparent, homogeneous and colored nanocomposite thin films and coatings for smart windows and solar technologies in a very short time (< 90s).

The development of phosphor devices free of heavy metal or rare earth elements is an important issue for environmental reasons and energy efficiency. Different mixtures of ZnO nanocrystals with Cs₂Mo₆I₈(OOC₂F₅)₆ cluster compound (CMIF) dispersed into polyvinylpyrrolidone matrix have been prepared by very simple and low cost solution chemistry. The resulting solutions have been used to fabricate highly transparent and luminescent films by dip coating free of heavy metal or rare earth elements. The luminescence properties of solution and dip-coated films were investigated. The luminescence of such a system is strongly dependent on the ratios between ZnO and CMIF amounts, the excitation wavelength and the nature of the system. By varying these two parameters (ratio and wavelength), a large variety of colors, from blue to red as well as white, can be achieved. In addition, differences in the luminescence properties have been observed between solutions and thin films as well as changes of CMIF emission band maximum wavelength. This may suggest some possible interactions between the different luminophore centers, such as energy transfer or ligands exchange on the Mo₆ clusters. Graphical Abstract