| Summary: | 碩士 === 國立中正大學 === 化學所 === 97 === This research focuses on chromogenic response for anion recognition based on ReI complexes. The reaction of Re(CO)5Cl with 4-mecaptopyridine (4-SNH) leds to the formation of [Re(CO)3(4-SNH)3]Cl (1), showing a characteristic LMCT (ligand-to-metal charge-transfer transition) transition. A variety of anions, i.e., CN-、OAc-、F-、Cl-、Br-、I-、PF6-、NO3-、ClO4-、and H2PO4-, as guests were used to study the host-guest chemistry of 1. Addition of CN- and OAc-, the spectral change in the absorption spectra is similar, but different from those of F-、Cl-、Br- and I-. No significant absorption change can be observed for the other anions. Finally, [Re(CO)3Cl(Py2S2)]2 (2, Py2S2 = 4,4’-dipyridyl disulfide) can be isolated and structurally characterized, where the crystals were grown from the solution of 1 with CN-. Thus, a deprotonation reaction is proceeded and following a S-S coupling reaction leading to the formation of 2. F-、Cl-、Br- and I- can be proposed to find H-bonding interactions with 1, whereas no signification interaction can be observed for the other anions.
In the second part, we design and synthesize a new ligand that has 1,4,7,10-tetraazacyclododecane (cyclen) and four pyridyl-amide moieties incorporated in the structural backbones, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrakis-ptridin-4-yl-amide (L) and 1,4,7,10-tetraaza-cyclododecane-1,4,7,10-tetrakis-ptridin-3-yl-amide (L’), as tetradentate ligand. Reactions of Zn(II) salts with L or L’ can give a series of Zn(II) coordination polymers, two-demensional [ZnCl2(L’)1/2]n (3) and [ZnBr2(L’)1/2]n (4) and three-dimensional [Cd(L)(NO3)]n (5), characterized by the X-ray diffraction analysis. Furthermore, we can conduct the metal-ion binding study by utilizing 3 and 5 as macrocyclic hosts toward various metal ions. The efficient luminescent quenching for solid samples of 3 and 5 can be observed, when 3 and 5 are immersed in the solutions containing Cu(II) ions. Thus, 3 and 5 can be useful sensory materials selective for Cu(II) ions.
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