We measure optical spectra of Nd-like W, Re, Os, Ir, and Pt ions of particular interest for studies of a possibly varying fine-structure constant. Exploiting characteristic energy scalings we identify the strongest lines, confirm the predicted 5s-4f level crossing, and benchmark advanced calculations. We infer two possible values for optical M2=E3 and E1 transitions in Ir 17þ that have the highest predicted sensitivity to a variation of the fine-structure constant among stable atomic systems. Furthermore, we determine the energies of proposed frequency standards in Hf 12þ and W 14þ . DOI: 10.1103/PhysRevLett.114.150801 PACS numbers: 06.20.Jr, 31.15.am, 31.15.bw, 32.30.Jc Highly charged ions (HCIs) are currently in the focus of theoretical studies analyzing their applications to frequency metrology and tests of a variation of the fine-structure constant α [1][2][3][4][5][6][7][8][9][10][11][12]. In most of the proposed HCIs with atomic number Z ¼ 55-98 and in charge states from 7 to 35, the complex electronic structures are experimentally unknown, and accurate calculations are extremely difficult. In view of novel techniques for sympathetically cooling HCIs in Paul traps [13][14][15] aiming at quantum logic spectroscopy on highly forbidden transitions [16], such data are urgently required.Observations from quasar absorption spectra have suggested a spatial variation of the value of the fine-structure constant α over cosmological dimensions [17], characterized by a dipolar distribution with a value of 10 −6 GLyr −1 . Laboratory experiments [18][19][20][21] have not yet reached the accuracy needed to test this dipolar pattern, which translates to a temporal variation of 10 −19 yr −1 [22] due to the motion of the Earth. Future optical clocks based on HCIs [3] could improve such tests. Interconfiguration transitions in HCIs have a high sensitivity to a variation of α due to large relativistic contributions to their binding energies. Advantageously, they have a strongly suppressed sensitivity to external perturbations [12]. However, interconfiguration transitions quickly shift from the optical laser range into the extreme ultraviolet or x-ray region with increasing charge state [23]. Nonetheless, at level crossings with two or more nearly degenerate electronic configurations, forbidden, and thus narrow, optical transitions with an enhanced sensitivity [1,2] arise. In particular, the Nd-like system Ir 17þ offers narrow lines between three electronic configurations 4f 14 , 4f 13 5s 1 , and 4f 12 5s 2 with the highest ever predicted sensitivity in a stable atomic system [2]. However, calculations for this system are exceptionally difficult, and the predicted energies for intraconfiguration M1 transitions ideally suited for clock applications [6] can exhibit errors on the 10% level, as can be seen below. For interconfiguration transitions, uncertainties at the eV level are expected. Thus, optical line identification becomes extremely difficult.In this Letter, we demonstrate a method to reliably identify transitions in...