The fair or good yield synthesis of new [(4.4)(n)]cyclophanes (n = 1-5), starting from 1,4-bis(2-hydroxymethyl-5,5-dimethyl-1,3-dioxan-2-yl)benzene and several diacid-dichlorides, based on monomer and oligomer formation reactions (from 1 + 1 to 5 + 5), is reported. The structure and the complex architectures of the lattices for these cyclophanes are revealed by the X-ray molecular structure for five compounds, NMR investigations, and mass spectrometry measurements. Intramolecular and intermolecular CH-pi, p-pi, and pi-pi interactions are observed, both in solid state and solution.
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http://dx.doi.org/10.1021/jo8006489 | DOI Listing |
Photochem Photobiol Sci
August 2024
Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University, Tsushima-Naka 3-1-1, Kita-Ku, Okayama, 700-8350, Japan.
[3](1,4)Naphthalenophanes, bearing carbon-bridge chains (syn- and anti-NPs) and nitrogen-bridge chains (syn- and anti-ANPs), were synthesized, and their X-ray structures and photoreactions were investigated. The intramolecular separation distance between the naphthalene cores for ANPs was shorter than that for NPs, suggesting that intramolecular interactions between the naphthalene rings were more efficient for ANPs compared to NPs. Upon photoirradiation at 300 nm, anti-NP, syn-ANP and anti-ANP produced the corresponding intramolecular [π4s + π4s] cycloadducts, whereas syn-NP gave an unidentified complex product mixture.
View Article and Find Full Text PDFAcc Chem Res
October 2020
Departamento de Química and Centro de Investigacións Científicas Avanzadas (CICA). Facultade de Ciencias, Universidade da Coruña, 15071, A Coruña, Spain.
Stoddart's "blue box" (), is one of the most iconic molecules in the recent history of chemistry. This rectangular tetracationic cyclophane has not only the ability to complex a wide variety of aromatic guests in organic or aqueous media, but because of the presence of viologen units on its structure, it also behaves as a redox-based molecular switch. In turn, -based host-guest complexes can translate this responsiveness from the molecular to the supramolecular level, resulting in host-controlled binding.
View Article and Find Full Text PDFJ Am Chem Soc
November 2019
Department of Chemistry , Northwestern University, 2145 Sheridan Road , Evanston , Illinois 60208 , United States.
The design and synthesis of artificial molecular switches (AMSs) displaying architectures of increased complexity would constitute significant progress in meeting the challenging task of realizing artificial molecular machines (AMMs). Here, we report the synthesis and characterization of a molecular shuttle composed of a cyclobis(paraquat-4,4'-biphenylene) cyclophane ring and a dumbbell incorporating a cyclobis(paraquat--phenylene) cyclophane "head" and a bifurcated, tawse-like "tail" composed of two oligoether chains, each containing a 1,5-dioxynaphthalene ring. In its reduced state the ring-in-ring recognition motif, between the and bisradical dicationic cyclophanes (rings), defines the [2]rotaxane, whereas in the oxidized state, the cyclobis(paraquat-4,4'-biphenylene) cyclophane encircles the two 1,5-dioxynaphthalene rings in the bifurcated "tail".
View Article and Find Full Text PDFJ Am Chem Soc
October 2019
Department of Chemistry , Zhejiang University, Hangzhou 310027 , P. R. China.
Organic radicals are of importance in developing smart materials that have paramagnetic and/or near-infrared optical properties. Their practical applications, however, are limited by the labile nature of the radicals. Here, we demonstrate that by using a tetracationic cyclophane, namely, cyclobis(4,4'-(1,4-phenylene)bispyridine--phenylene) (), to encapsulate a naphthalenediimide (NDI) guest, the redox properties of NDI can be modulated.
View Article and Find Full Text PDFInorg Chem
February 2019
Institute of Chemistry and Life Science , Changchun University of Technology Changchun, Jilin 130012 , P. R. China.
Five unique Keggin-type polyoxometalate (POM)-based metal-organic frameworks (POMFs), namely [CHL1][(CuL1)(PMoMoO)] (1), [Zn(HO)(L1)][Zn(L1)Cl][HL1][PMoO]·1.25HO (2), (TBA)[Cu(HO)L1][PMoO] (3), [Cu(HO)(L1)][PMMoO] (4), (HL2)[(CuL2)(PMoO)]·HO (5), L1 = 4,4'-bis((1H-1,2,4-triazol-1-yl)methyl)-biphenyl, L2 = 1,4-bis((1H-1,2,4-triazol-1-yl)methyl)-benzene, have been synthesized under ionothermal conditions. According to single-crystal data, 1 exhibits a novel mechanically interlocked molecular architecture (MIMA) constructed by two-dimensional (2D) interpenetrating polyrotaxane layers with unique cyclophanes (tetra-cationic viologen macrocycle cyclobis(paraquat- p-phenylene) (CBPQT system)), resulting in an H-bonded 3D supermolecule, and is the first synthesis of self-assembled cyclophane-PMOFs under ionothermal conditions.
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