Group-5 transition metal ditellurides Te ( = V, Nb, Ta) are unique CdI-type layered materials that exhibit peculiar quasi-one-dimensional intralayer superstructures, known as ribbon-chains and butterfly-like clusters of atoms. In this review article, we attempt to systematically understand their electronic band structures based on our recent angle-resolved photoemission spectroscopy (ARPES) studies and first-principles calculations. We underscore the role of the localized molecular-like orbital bonds that form the anomalous flat bands in the momentum space, and demonstrate how they influence the Fermi surface anisotropy, phase stabilities of crystal structures, and nontrivial topological properties in some cases. We also elaborate the future prospects for novel quantum phenomena that can be realized in these materials.

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