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제129회 대한화학회 학술발표회, 총회 및 기기전시회 Formation of Zn(II) Supramolecular Isomers and Their Photoreactivity

등록일
2022년 1월 17일 11시 30분 06초
접수번호
0025
발표코드
INOR.P-100 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
발표시간
4월 15일 (금요일) 11:00~13:00
발표형식
포스터
발표분야
Inorganic Chemistry
저자 및
공동저자
Jaewook An, Dong Hee Lee, In-Hyeok Park*
Graduate School of Analytical Science and Technology, Chungnam National University, Korea
Supramolecular isomers have a same chemical formula but more than one crystal structure in coordination polymers (CPs) and metal-organic frameworks (MOFs).[1] Here we report the significant correlation of solvents, coordination environments, and photoreactivity between two Zn(II) supramolecular isomers. A 1D zigzag CP, [Zn(bpe)(adc)2] (1) is synthesized under solvothermal reaction of Zn(NO3)2·6H2O, 1,2-bis(4-pyridyl)ethylene (bpe), and 1-adamantanecarboxylic acid (Hadc) in a mixture of dimethylacetamide (DMA) and H2O. The mononuclear repeating unit in 1 consists of one Zn(II) atom, two bpe ligands, and two adc ligands. Zn1 atom is pseudo-tetrahedrally coordinated by two nitrogen atoms of bpe ligands and four oxygen atoms of adc ligands. On the other hand, a 1D railroad CP, [Zn(bpe)(adc)2] (2) is synthesized by same reaction condition except dimethylformamide (DMF) instead of DMA. The dinuclear repeating unit in 2 consists of two Zn(II) atoms, four bpe ligands, and four adc ligands. Zn1 is octahedrally coordinated by two nitrogen atoms of bpe ligands and four oxygen atoms of adc ligands. Especially, the double bonds of bpe ligands in 2 are parallelly aligned to each other at a distance of 3.6 Å. According to Schmidt’s Criteria,[2] while the distance of olefins is within the range of 3.6-4.1 Å, olefins can be photo-dimerized by UV irradiation. 1H nuclear magnetic resonance (NMR) spectrum of the crystals obtained after irradiation of 1 under UV for 48 h showed the formation of cyclobutane peaks at 5.3 ppm. For better understanding of the irradiated crystal structure, we attempted to receive suitable single crystals for single crystal X-ray diffraction analysis (SC-XRD). The X-ray crystal structure of the photodimerized CP [Zn(rctt-tpcb)(adc)2] (3, rctt = regio, cis, trans, trans; tccb = 1,2,3,4-tetrakis(3’-carboxyphenyl)-cyclobutane) was finally confirmed by SC-XRD. To monitor the homogeneity of 1 and 2, the powder X-ray diffraction (PXRD) patterns have also been investigated. The details will be presented at the poster section.

References

[1] T. L. Hennigar, D. C. MacQuarrie, P. Losier, R. D. Rogers, M. J. Zaworotko, Angew. Chem. Int. Ed. Engl. 1997, 109, 972-973.

[2] G. M. J. Schmidt, Photodimerization in the solid state, Pure Appl. Chem., 1971, 27, 647-678.