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Electronic coupling can be used to tailor electronic states and optical properties of the luminophores. Therefore, electronically coupled systems would provide unique properties, which cannot be achieved by individual constituents. Here, electronically coupled gold nanoclusters (AuNCs) were prepared on the basis of organosilane grafting and a sol-gel-derived porous silica template. After prolonged drying, the formed AuNCs@silica composites exhibited red-shifted, line-width-narrowed, deep-red emission with high quantum yields (QYs) of ∼6