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Quantum dot (QD) solids are being widely exploited as a solution-processable technology to develop photovoltaic, light-emission, and photo-detection devices. Charge transport in these materials is the result of a compromise between confinement at the individual QD level and electronic coupling among the different nanocrystals in the ensemble. While this is commonly achieved by ligand engineering in colloidal-based systems, ligand-free QD assemblies have recently emerged as an exciting alternative where nanostructures can be directly grown into porous matrices with optical quality as well as control over their connectivity and hence charge transport properties. In this context, we present a complete photophysical study comprising fluence and temperature-dependent time-resolved spectroscopy to study carrier dynamics in ligand-free QD networks with gradually varying degrees of interconnectivity, which we achieve by changing the average distance between the QDs. Analysis of the photoluminescence and absorption properties of the QD assemblies, involving both static and time-resolved measurements, allows us to identify the weight of the different recombination mechanisms, both radiative and non-radiative, as a function of QD connectivity. We propose a picture where carrier diffusion, which is needed for any optoelectronic application and implies inter-particle transport, gives rise to the exposure of carriers to a larger defect landscape than in the case of isolated QDs. The use of a broad range of fluences permits extracting valuable information for applications demanding either low or high carrier injection levels and highlighting the relevance of a judicious design to balance recombination and diffusion.