(abridged) We present the X-ray analysis of a sample of 30 luminous quasars at $zsimeq3.0-3.3$ with deep XMM-Newton observations, selected from the SDSS-DR7 to be representative of the most luminous, intrinsically blue quasar population. By construction, the sample boasts a unique degree of homogeneity in terms of optical/UV properties. In the X-rays, only four sources are too faint for a detailed spectral analysis. Neglecting a radio-loud object, the other 25 quasars are, as a whole, the most X-ray luminous ever observed, with rest-frame 2-10 keV luminosities of $0.5-7times10^{45}$ erg/s. The continuum photon index distribution, centred at $Gammasim1.85$, is in excellent agreement with those in place at lower redshift, luminosity and black-hole mass, confirming the universal nature of the X-ray emission mechanism in quasars. Even so, when compared against the well-known $L_{rm X}-L_{rm UV}$ correlation, our quasars unexpectedly split into two distinct subsets. About 2/3 of the sources are clustered around the relation with a minimal scatter of 0.1 dex, while the remaining 1/3 appear to be X-ray underluminous by factors of $>3-10$. Such a large incidence ($approx25%$) of X-ray weakness has never been reported in radio-quiet, non-BAL quasar samples. Several factors could contribute to enhance the X-ray weakness fraction among our $zsimeq3$ blue quasars. However, the X-ray weak objects also have, on average, flatter spectra, with no clear evidence of absorption. Indeed, column densities in excess of a few $times10^{22}$ cm$^{-2}$ can be ruled out for most of the sample. We suggest that, at least in some of our X-ray weak quasars, the corona might experience a radiatively inefficient phase due to the presence of a powerful accretion-disc wind, which substantially reduces the accretion rate through the inner disc and so the availability of seed photons for Compton up-scattering.
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