Recent developments of the multiplex paradigm included efforts to understand the role played by the presence of several layers on the dynamics of processes running on these networks. The possible existence of new phenomena associated to the richer topology has been discussed and examples of these differences have been systematically searched. Here, we show that the interconnectivity of the layers may have an important impact on the speed of the dynamics run in the network and that microscopic changes such as the addition of one single inter-layer link can notably affect the arrival at a global stationary state. As a practical verification, these results obtained with spectral techniques are confirmed with a Kuramoto dynamics for which the synchronization consistently delays after the addition of single inter-layer links.The ubiquity of processes naturally described by dynamics on networks raises important issues on the role played by network structure on the emergence of collective phenomena. It has been shown that spectral analysis of the associated adjacency and Laplacian matrices can offer insights into a variety of fundamental phenomena such as those relying upon spreading or diffusion mechanisms [1][2][3]. In particular, spectral methods are the basis to characterize synchronization and random walk diffusion in networks [4][5][6][7]. The second smallest eigenvalue λ 2 is known to be related to the timescale to synchronization [8] and consensus [9], and is often interpreted as the 'proper time' of the system to relax [10]. This quantity, which depending on the literature is known as 'algebraic connectivity' or 'spectral gap', is also indicative of the time of diffusion [11]. While the role of λ 2 in "simple" graphs is well understood, more effort is needed to characterize its role and behavior in more realistic (and therefore complex) contexts.One such novel framework is that of a multilayer network [12][13][14]. Its usefulness extends from finance [15][16][17] and mobility [18,19], to epidemics [20,21] and societal dynamics [22][23][24][25][26][27][28]. The multiplex scenario is ostensibly non-trivial, in the sense that the phenomena observed on this system of interconnected networks cannot be straightforwardly reduced to an aggregate network [29]. The implication is that the multiplex structure plays a fundamental role in diffusive processes, and that therefore its effect of on λ 2 is a pertinent and open issue.Diffusion on a multiplex, that is, a system with layers of N nodes with an association of corresponding nodes in each layer, were considered in [30,31]. By varying the inter-layer diffusion constant, these works found boundaries of λ 2 for the multiplex in terms of the values for individual layers (see also [32]). For a general weighted two-layer multiplex with a varying inter-layer link weight p, these results were rephrased in terms of a structural transition [33]: it was found that below some critical p c , λ 2 (p) ∼ 2 p, while for larger p the algebraic connectivity approaches an asymptote given...