The critical temperatures, T-c, of CO2, CH4, and Ar are 304 K, 191 K, and 151 K, respectively. This paper highlights some unusual characteristics of adsorption and diffusion of these molecules in microporous structures such as zeolites and metal organic frameworks at temperatures T < T-c. Published experimental adsorption data for T < T-c show that the isotherms invariably display stepped characteristics. The inverse thermodynamic factor 1 /Gamma(i) equivalent to d ln c(i)/d ln f(i) exceeds unity for a range of fugacities f(i) and molar concentrations c(i) within the pore corresponding to the steep portion of the isotherm. With the aid of Monte Carlo simulations of isotherms for different temperatures T T-c in a variety of zeolites (AFI, MTW, FAU, NaY, MR, and MOR), metal-organic Frameworks (IRMOF-1, CuBTC, MIL-47 (V), and MIL-53 (Cr)), and covalent-organic frameworks (COF-102, and COF-108), we investigate the conditions required for 1/Gamma(i) > 1. For each of the three species investigated, data on pore concentrations c(i) at any given temperature below T-c fall within the binodal region for the hulk fluid phase. We present evidence to suggest that, in the concentration ranges for which 1/Gamma(i) > 1, clustering of molecules occurs. The extent Of Clustering is enhanced as T falls increasingly below T, Furthermore, Molecular dynamics simulations of diffusion demonstrate that the concentration dependence of the diffusivities is markedly influenced in the regions where 1/Gamma(i) > 1. In regions where molecular Clustering Occurs, the Fick diffusivity Shows, in some cases, a decreasing trend with concentration.