초록

- 새로운 황 거대고리를 빌딩블럭으로 사용하여 Pd/Ag의 이핵을 갖는 새로운 이차원 배위고분자를 제조하고, 그 결정구조를 규명하였음
- 황 거대고리에 카바졸 형광기를 결합시켜 새로운 개념의 나노형광센서를 제조하였으며, 특히 이 센서물질은 Hg(II)에 대해 높은 Turn-Off형 선택성을 보였음

Abstract ▼

Sulfur-containing macrocyclic receptors and their heavy metal complexes with diverse types of supramolecular coordination polymeric structures have been synthesized and structurally characterized. Based on these results, macrocycle-type fluorescence sensing materials have been synthesized and their

Sulfur-containing macrocyclic receptors and their heavy metal complexes with diverse types of supramolecular coordination polymeric structures have been synthesized and structurally characterized. Based on these results, macrocycle-type fluorescence sensing materials have been synthesized and their performance for the detection of heavy metal species was investigated. The proposed single-molecule type based sensors are expected that their performance could be improved by irradiation of proton beam. First, a range of thiaphilic mononuclear ($Hg^{2+}$+and $Ag^+$) and heterobinuclear ($Ag^+$/$Pd^{2+}$) complexes (1-6) of an $NS_2$2-donor macrocycle L with discrete and networked forms were prepared and structurally characterized. Reaction of L with $HgC_{12}$ afforded a unique 1:1 (cationic/anionic) complex $[Hg_2(L) Cl_5][Hg(_L)Cl]$ (1). Reaction of L with $Hg(ClO_4)_2$ yielded the sandwich-type 1:2 (metal-to-ligand) complex $[Hg(L)_2](ClO_4)_2$ (2). Contrasting with the mercury(II) salts, the reactions of L with AgX ($X={NO_3}^-$ and ${CF_3SO_3}^-$) yielded an isostructural one-dimensional (1D) zigzag networks[Ag(L)X]n ($X={NO_3}^-$ and 4; $X={CF_3SO_3}^-$) in which each ring of L is exo-coordinated via two S atoms and one N atom to a silver ion which is also bound to one S atom in the neighboring L such that the overall coordination geometry about each silver is four-coordinate. Whereas, reaction of L with $K_2PdCl_4$ gave a discrete exocyclic complex 5, $[cis-Cl_2Pd(L)]$. Through a successive reaction of the complex 5 with $AgNO_3$, a heterobinuclear two-dimensional (2D) coordination polymer 6, $[Pd(L)Ag_{2.5}(NO_3)_{4.5}(H_2O)_{0.5}]_n$, utilizing exocyclic Pd(II) and Ag(I) was isolated and characterized. In extension of above works, $NS_2O_2$-type macrocyclic receptor was synthesized as a recognition unit for the detection of specific heavy metal species. Novel chemosensor L' was prepared by linking the carbazole unit as a fluorophore to the recognition unit. The proposed L' showed high selectivity for Hg(II) among the various metal species by means of strong CHEQ (chelation-enhanced fluorescence quenching) effect.

목차 Contents

• 표지...1
• 제출문...2
• 보고서 요약서...3
• 요약문...4
• SUMMARY...5
• 목차...7
• 제1장 연구개발과제의 개요...8
• (1) 연구개발의 목적...8
• (2) 연구개발의 필요성...8
• 제2장 국내외 기술개발 현황...9
• (1) 세계적 수준...9
• (2) 국내수준...9
• 제3장 연구개발수행 내용 및 결과...10
• 1) NS2-거대고리의 불연속 수은(II) 착물 및 일차원 그리고 팔라듐(II)을 매개로 한 이차원 은(I) 배위고분자의 제조 및 구조적 특성...10
• 2)제2절 형광성 수용체의 분자설계, 합성 및 센서 특성평가...16
• 제4장 목표달성도 및 관련분야에의 기여도...19
• 제5장 연구개발결과의 활용계획...20
• 가. 경제적 측면...20
• 나. 사회적 측면...20
• 다. 기술적 측면...20
• 제6장 연구개발과정에서 수집한 해외과학기술정보...21
• 제7장 참고문헌...22