Phonon frequency comb close to an isolated Einstein mode in [Formula: see text].

The emergence of phonon frequency combs exemplifies a rare and intriguing phenomenon in quantum solids. Materials with distinctive phonon band structures are especially promising for hosting such states, as their vibrational dispersion landscape across the Brillouin zone can facilitate the formation of long-lived, collective lattice excitations. In the layered Van der Waals compound [Formula: see text], polarization-resolved Raman spectroscopy reveals a pronounced anharmonicity in symmetry-predicted modes and the formation of a self-organized frequency domain structure (coherent-like state), in the range of a localized high-energy [Formula: see text] phonon mode near 500 cm-1. This strong phonon-phonon coupling manifests itself as an anomalous temperature dependence around 200 K, coinciding with the appearance of higher-order excitations within the phonon density of states gap. These findings position [Formula: see text] as an unconventional platform where intrinsic highly structured phonon spectral correlations and unusually strong anharmonic effects coexist, opening new avenues for exploring emergent vibrational phenomena in low-dimensional materials.