Aminoquinonato bridged Re(I)-based metallarectangles have been constructed via an orthogonal bonding approach. Self-assembly of Re-2(CO)(10) and aminoquinone ligands in the presence of ditopic linear pyridyl ligands has resulted in the formation of metallarectangles of the general formula [{(CO)(3)Re(mu-eta(4)-L)Re(CO)(3)}(2)(mu-N-L'-N)(2)] (1-4), wherein 1, L = 2,5-bis(n-butylamino)-1,4-benzoquinonato (bbbq) and N-L'-N = 4,4'-bipyridine (bpy); 2, L = 2,5-bis(phenethylamino)-1,4-benzoquinonato (bpbq) and N-L'-N = 4,4'-bipyridine; 3, L = 2,5-bis(n-butylamino)-1,4-benzoquinonato (bbbq) and N-L'-N = trans-1,2-bis(4-pyridyl)ethylene (bpe) and 4, L = 2,5-bis(phenethylamino)-1,4-benzoquinonato (bpbq) and N-L'-N = trans-1,2-bis(4-pyridyl)ethylene (bpe). Metallarectangles 1-4 have been characterized by elemental analysis, IR, NMR, and UV-vis absorption spectroscopic techniques. The molecular structures of 1 and 4 were determined by single-crystal X-ray diffraction methods. The molecular recognition capability of 1 and 3 with pyrene and triphenylene has been investigated using UV-vis absorption and emission spectroscopic techniques. The formation of host guest complex has been further corroborated by the single-crystal X-ray structural evidence of carceplex system (3Dpyrene).(DMF).