Active apolar doping determines routes to colloidal clusters and gels.

Collections of interacting active particles, self-propelling or not, have shown remarkable phenomena including the emergence of dynamic patterns across different length scales, from animal groups to vibrated grains, microtubules, bacteria, and chemical- or field-driven colloids. Burgeoning experimental and simulation activities are now exploring the possibility of realizing solid and stable structures from passive elements that are assembled by a few active dopants. Here we show that such an elusive task may be accomplished by using a small amount of apolar dopants, namely synthetic active but not self-propelling units. We use blue light to rapidly assemble 2D colloidal clusters and gels via nonequilibrium diffusiophoresis, where microscopic hematite dockers form long-living interstitial bonds that strongly glue passive silica microspheres. By varying the relative fraction of doping, we uncover a rich phase diagram including ordered and disordered clusters, space-filling gels, and bicontinuous structures formed by filamentary dockers percolating through a solid network of silica spheres. We characterize the slow relaxation and dynamic arrest of the different phases via correlation and scattering functions. Our findings provide a pathway toward the rapid engineering of mesoscopic gels and clusters via active colloidal doping.