Two coordination polymers with formulas [CuI(dapym)]n and [Cu2I2(dapym)]n (dapym = 2,4-diaminopyrimidine) have been synthesized in water at room temperature. According to the stoichiometry used, mono (1D) and the two-dimensional (2D) structures can be obtained. Both are made up of Cu2I2 double chains. Their high insolubility in the reaction medium also makes it possible to obtain them on a nanometric scale. Their structural flexibility and short Cu-Cu distances provoke interesting optoelectronic properties and respond to physical stimuli such as pressure and temperature, making them interesting for sensor applications. The experimental and theoretical studies allow us to propose different emission mechanisms with different behaviors despite containing the same organic ligand. These behaviors are attributed to their structural differences. The emission spectra versus pressure and temperature suggest competencies between different transitions, founding critical Cu2I2 environments, i.e., symmetric in the 1D compound and asymmetric for the 2D one. The intensity in the 2D compound's emission increases with decreasing temperature, and this behavior can be rationalized with a structural constriction that decreases the Cu-Cu and Cu-I distances. However, compound 1D exhibits a contrary behavior that may be related to a change of the organic ligand's molecular configuration. These changes imply that a more significant Π-Π interaction counteracts the contraction in distances and angles when the temperature decreased. Also, the experimental conductivity measurements and theoretical calculations show a semiconductor behavior. The absorption of the 1D compound in UV, its intense emission at room temperature, and the reduction to nanometric size have allowed us to combine it homogeneously with ethyl vinyl acetate (EVA), creating a new composite material. The external quantum efficiency of this material in a Si photovoltaic mini-module has shown that this compound is an active species with application in solar cells since it can move the photons of the incident radiation (UV region) to longer wavelengths.