Coupling between tuneable broadband modes of an array of plasmonic metamolecules and a vibrational mode of carbonyl bond of poly(methyl methacrylate) is shown experimentally to produce a Fano resonance, which can be tuned in situ by varying the polarization of incident light. The interaction between the plasmon modes and the molecular resonance is investigated using both rigorous electromagnetic calculations and a quantum mechanical model describing the quantum interference between a discrete state and two continua. The predictions of the quantum mechanical model are in good agreement with the experimental data and provide an intuitive interpretation, at the quantum level, of the plasmon-molecule coupling.PACS numbers: 73.20. Mf, 78.67.Pt, 78.68.+m, 42.82.Et, The spectral control of optical absorption in metallic nanostructures has generated rapidly growing interest, both as a means for studying light-matter interaction at the deep-subwavelength scale and to develop new functional nanomaterials. Plasmonic materials provide an ideal platform for achieving enhanced optical interaction at the nanoscale as their primary building blocks consist of highly resonant particles, which strongly confine and enhance the optical field [1][2][3][4]. These properties are commonly employed to increase the optical coupling between plasmonic structures and an optically active medium, enabling many applications, including surface-enhanced Raman spectroscopy [5,6], surface-enhanced infrared absorption spectroscopy [7,8], enhancement of the excitation rate and fluorescence of quantum dots (QDs) and molecules [9][10][11], chemical sensing [12,13], and biodetection [14,15]. One effective approach for tailoring the shape of plasmonic resonances is the Fano interference between a narrow (discrete) resonance and a broad (continuous) one [16][17][18][19].A defining feature of Fano resonances is their pronounced spectral asymmetry. This can be exploited in applications that require high sensitivity to changes in the environment. Fano resonances in plasmonic systems can also provide physical insights into light-matter interaction at the nanoscale, as they are primarily the result of short-range, near-field interactions. Although Fano resonances in plasmonic systems have been chiefly investigated in a classical context, they can also be observed in quantum systems consisting of QDs, atoms, or molecules coupled to metallic nanoparticles [14,[20][21][22]. In this case the Fano resonance results from the interaction between a quantum discrete state and a classical continuum (localized or extended) plasmon mode. In many applications it is desirable to tune the strength of the interaction between the discrete and continuous state, and consequently dynamically change the shape of Fano resonances. However, since the materials and geometrical parameters of a plasmonic structure are difficult to control at the nanoscale, a convenient way to achieve optical tunability has not yet been attained.In this Letter we demonstrate experimentally and theoretica...