Despite that it is more than 100 years since the atomic nucleus was first dis- covered by Ernest Rutherford and coworkers, many of its features still elude our understanding. The fact that the fundamental interactions between the nuclear constituents; nucleons, and ultimately quarks, are not yet known in detail, and the complexity of the nuclear many-body system compound the great challenges facing theoretical interpretations of experimental data. It is therefore important to focus on distinct phenomena where experimental mea- surements can be compared with theoretical predictions, providing stringent tests of theory. One such area is the nuclear phenomenology of collective excitations related to rotations and vibrations of the nucleus as a whole, and how such modes of excitation may develop from the interactions between a few nucleons occupying single-particle orbits outside closed shells.This thesis is devoted to experimental studies of excited states in the 99Tc, 162W, and 166Re nuclei. These nuclei lie in “transitional” regions of the Segre chart, where collective excitation mechanisms start becoming important when adding valence nucleons outside closed neutron and proton shells. Such nuclei are important for testing state-of-the-art theoretical models. The excited states of the nuclei studied in the present work were populated using heavy-ion fusion-evaporation reactions. Prior to the present work, high-spin data were still lacking in 99Tc since in the previous works [1–5] excited states were only populated up to around 3 MeV. Two collective bands have been extended to intermediate angular momentum states in the present work. The experimental results were compared with the systematics of other technetium isotopes, evaluating electromagnetic characteristics based on semiclassical calculations and the particle-rotor model. The 162W and 166Re nuclei are situated in the very neutron-deficient 160-170 mass region, requiring special techniques for identifying their excited-state structures. The level scheme of 162W was first reported by Dracoulis et al. in 1993 [6], where the first excited 2+ state was assigned to be 450 keV above the ground state. However, the lack of selectivity made the γ-ray identification for higher energy levels of 162W uncertain. In this work, the highly selective recoil-decay tagging technique was used to uniquely identify γ-ray transitions from excited states in 162W and to construct its level scheme. In addition, the experimental setup enabled a precise determination of the half-life of the α-decaying ground state of 162W. The α-formation probability for 162W was extracted from the measurement of the half-life and systematical comparisons with the neighboring nuclei were performed. Two rotational-like bands were identified in 166Re for the first time and the lifetimes of the lowest three excited states in band (1) were measured using the recoil distance Doppler shift method. The results were compared with theoretical calculations based on a semiclassical approach, the particle-rotor model, and the tilted axis cranking model in a relativistic mean field approach. The microscopic mechanisms (configuration and alignment, etc) of the rotational bands were interpreted under the framework of total Routhian surface predictions and cranked shell model calculations.