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A family of neutral, heteroleptic, dinuclear M2LL'-type pentagonal toroid-shaped metallomacrocycles (1-8) were synthesized using flexible ditopic N donors (Ln = L1-L2), rigid bis-chelating ligands (H2-L' = H2-E), and Re2(CO)10 in a one-pot solvothermal self-assembly approach. The ligands and the metallomacrocycles were characterized using ATR-IR, electrospray ionization mass spectrometry, nuclear magnetic resonance, ultraviolet-visible, and emission spectroscopy methods. The molecular structures of 1, 2, 4, 6, and 7 were confirmed by an X-