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Selective Binding of Open Frameworks Assembled from Nickel(II) Macrocyclic Complexes with Organic and Inorganic Guests
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Selective Binding of Open Frameworks Assembled from Nickel(II) Macrocyclic Complexes with Organic and Inorganic Guests
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Journal Article
Selective Binding of Open Frameworks Assembled from Nickel(II) Macrocyclic Complexes with Organic and Inorganic Guests
2001
Overview
Inclusion studies for metal-organic open-frameworks, [Ni(C10H24N4)(H2O)2]3[BTC]2·24H2O (1) and [Ni(C10H26N6)]3 [BTC]2·18H2O(2) (BTC3- = 1,3,5-benzenetricarboxylate) with various organic andinorganic guest molecules have been carried out. 1 is the previously reportedmolecular floral lace with 1-D channels, where positively charged macrocyclic layersand negatively charged BTC3- layers are alternately packed by hydrogen bondinginteractions. 2 is assembled in this study from nickel(II) hexaazamacrocyclic complexcontaining methyl pendant arms and BTC3-. The X-ray structure of 2 shows thatthe nickel(II) complex and BTC3- form a 2-D coordination polymer. The XRPD patternsof 2 indicate that framework of 2 is slightly deformed upon removal of waterguest molecules but restored upon rebinding of water. The host solid 1 binds MeOHin toluene, and 1,3,5-trihydroxybenzene (THB) and 4-hydroxyacetophenone (HAP) in EtOH/toluene (v/v = 1/4) solutions. The binding constants (Kf) of 1 forMeOH, THB, and HAP are 66.4 M-1, 259 M-1, and 13.9 M-1,respectively. In the range of high concentration of the guest, however, the host showsvarious binding curves depending upon the types of guest. It binds PhOH in toluene,showing a sigmoid curve. It also binds transition metal complexes such as[Cu(NH3)4](ClO4)2, [Cu(ethylenediamine)2](ClO4)2,[Cu(histamine)2](ClO4)2, and[Cu(N,N'-bis(3-aminopropyl)ethylenediamine)](ClO4)2 in MeCN, with Kf values of 645 M-1, 9.52 M-1, 37.2 M-1, and 6.00 M-1,respectively. The host solid 2 binds selectively PhOH over PhCl and PhBr, showing that hydrogen bonding interaction between the host and guest plays an important role in the selectivity.
Publisher
Springer Nature B.V
