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Nitrobenzene을 guest로 포접한 3차원 금속착체 포접화합물의 결정구조
박기민,박상윤,이욱,이와모토 토시타케,Park, Ki-Min,Park, Sang-Yun,Lee, Uk,Iwamoto, Toschitake 대한화학회 1996 대한화학회지 Vol.40 No.7
3차원 금속착체 포접화합물 $Cd(pn)Ni(CN)_4{\cdot}0.5NO_2C_6H_5$(pn: 1,2-diaminopropane=propylenediamine)은 사방정계 공간군 $Pn2_1$a로, a=13.868(5), b=26.591(4), c=7.840(1)${\AA}$, V=2891(1)${\AA}^3$, Z=4이며, 28000개의 독립적인 회절반점에 대한 R값은 0.054이다. 이 포접화합물의 host구조는 가지 달린 지방족 guest 분자를 포접한 포접화합물의 host 구조(T-type)와 같다. Nitrobenzene guest 분자는 T-type의 nodal형 턴넬속에 안정하게 포접되는데, 이는 node 위치체 pn-amino group이 놓이고, antinode 위치에 부피가 큰 방향조 고리가 놓이며, 이들 사이에 극성인 nitro group이 있기 때문이다. 턴넬형의 포접골간을 갖는 금속착체 $Cd(pn)Ni(CN)_4$의 host 구조가 가지 달린 방향족 guest 분자를 포접하고 있다. The three-dimensional metal complex inclusion compound $Cd(pn)Ni(CN)_4{\cdot}0.5NO_2C_6H_5$(pn: 1,2-diaminopropane=propylenediamine) crystallizes in the orthorhombic space group, $Pn2_1$a, (a=13.868(5), b=26.591(4), c=7.840(1)${\AA}$, V=2891(1)${\AA}^3$, Z=4), R=0.054 for 2800 independent reflections. The host structure of the inclusion compound appears the same one(T-type) of inclusion compound with branched aliphatic-guest molecule. The nitrobenzeneguest molecule attains the stable position in the nodal channel of T-type by placing the polar nitro group between the pn-amino groups at the node and the bulky aromatic ring in the antinodal zone of the channel. The substituted aromatic guest molecule is accommodated in the host structure of metal complex $Cd(pn)Ni(CN)_4$ with channel cavity.
Physicochemical Properties of Protoporphyrin IX by Metal Ions in Acetonitrile-Water Mixture Solution
박기민,Jeong-Im Yang,Ho-Suk Lee,이지범,박철호,박형련 대한화학회 2010 Bulletin of the Korean Chemical Society Vol.31 No.6
The UV-vis absorption spectrum of protoporphyrin IX shows a very sharp and strong absorption maximum peak at 398nm in acetonitrile-water mixture solution (1:1 v/v). When divalent metal ions such as Cu2+, Zn2+, and Ca2+ ion were added to protoporphyrin IX, metal protoporphyrin IX complexes were thereby produced. Cu-protoporphyrin IX complexes have the largest formation constant (Kf) among them. The fluorescence intensity of protoporphyrin IX was diminished by the presence of Cu2+, Zn2+, Ca2+, Mn2+, and Ni2+ ions as quenchers. However, Mg2+, Mn2+, and Ni2+ ions are hardly combined with protoporphyrin IX. Mg2+ ion does not take part in the fluorescence quenching process of protoporphyrin IX in acetonitrile-water mixture solution. According to the Stern-Volmer plots, fluorescence quenching by Cu2+, Zn2+,and Ca2+ ions involves static quenching, which is due to complex formation. On the contrary, dynamic quenching has a large influence on the overall quenching process, when Mn2+ and Ni2+ ions were added to protoporphyrin IX in acetonitrile-water mixture solution.