Two high-spin Fe­(II) and Co­(II) complexes of 1,4,7,10-tetraazacyclododecane (CYCLEN) appended with four 2-amino-6-picolyl groups, denoted as Fe­(TAPC)2+ and Co­(TAPC)2+, are reported. These complexes demonstrate C 2-symmetrical geometry from coordination of two pendents, and they are present in a single diastereomeric form in aqueous solution as shown by 1H NMR spectroscopy and by a single-crystal X-ray structure for the Co­(II) complex. A highly shifted but low-intensity CEST (chemical exchange saturation transfer) signal from NH groups is observed at −118 ppm for Co­(TAPC)2+ at pH 6.0 and 37 °C. A higher intensity CEST peak is observed for Fe­(TAPC)2+, which demonstrates a pH-dependent frequency shift from −72 to −79 ppm at pH 7.7 to 4.8, respectively, at 37 °C. This shift in the CEST peak correlates with the protonation of the unbound 2-amino-6-picolyl pendents, as suggested by UV–vis and 1H NMR spectroscopy studies at different pH values. Phantom imaging demonstrates the challenges and feasibility of using the Fe­(TAPC)2+ agent on a low-field MRI scanner. The Fe­(TAPC)2+ complex is the first transition-metal-based paraCEST agent that produces a pH-induced CEST frequency change toward the development of probes for concentration-independent imaging of pH.