FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2012608710> ?p ?o ?g. }

• W2012608710 endingPage "382" @default.
• W2012608710 startingPage "369" @default.
• W2012608710 abstract "The cooperative nature of non-covalent interactions which give rise to inclusion complexes involving cyclobis(paraquat-p-phenylene), 14+, and related cyclophane derivatives, 24+–44+, with substituted 1,4-phenyl and 4,4′-biphenyl guests has been studied by spectroscopic techniques and ab initio and semiempirical molecular orbital methods. Inclusion complex formation and stability are primarily determined by the combination of two main interaction modes involving aromatic stacking of the guest within the cyclophane cavity and external interactions between guest side arms and the exterior of the cyclophane. A balance between cavity and external forces results in supramolecular association and is shown to change depending upon the functionality and substitution of the guest. Cavity binding was probed using 1,4-phenyl and 4,4′-biphenyl guests, where for the 1,4-phenyl guests the primary basis for energy stabilization with 14+ is found to be short-range stabilizing electrostatic forces complemented by small amounts of polarizability and charge-transfer. In contrast, the cavity binding between substituted 4,4′-biphenyl guests and 14+ is determined by almost equal contributions of polarizability and electrostatics. The effect of solvent is shown to have only a small effect on the computed geometry of 14+ complexes, but its impact upon binding energies is substantial. The first solvation shell of the cyclophanes is computationally approximated by 12 acetonitriles and satisfies the requirements of the 16 relatively acidic protons on the bipyridinium groups. Good correlations between the computed (with solv ation) and experimental 14+ binding energies are found. The degree of linear correlation improves substantially when the comparison between computed and experimentally observed binding energies is restricted to structurally similar (number of aromatic rings, number of substituents and position of substitution) molecular guests. Furthermore, computed molecular properties, such as polarizability, maximum hardness, softness and electronegativity of the isolated guests, correlate well with 14+ binding energies based upon the same requirement of guest similarity. The non-covalent forces associated with the external cyclophane interactions were studied with guest molecules built from symmetrical 1,4-extensions of hydroquinone composed of aliphatic or ethyleneoxy side arms. In particular, side arm length and functionality, and the position and type of heteroatoms along the chain, were systematically varied to define the external interactions between the guest side arms and different host cyclophanes. Specifically, the ethyleneoxy linkages are shown to provide a large chelate and cooperative effect which direct the binding with 14+. In order to probe further the special geometric and electronic character of 14+, we have synthesized and tested a new supramolecular host, 24+, similar to 14+ but where a pentacycloundecane unit replaces one of the xylyl groups. Both experimental and computed data on the new host emphasize the ideal geometry and electronic nature of the 14+ molecular receptor for aromatic guests. The inclusion complexes discussed in this paper are important not only because they, or similar entities, are the main components of many rotaxanes, catenanes and other switchable molecules, but because the intermolecular interactions involved, such as electrostatics, polarizability and charge-transfer, are ubiquitous in supramolecular chemistry. The information reported on the specific interactions involving the 14+–44+ molecular receptors with substituted aromatic guests can also be extended by analogy to many systems of broad interest. © 1997 John Wiley & Sons, Ltd." @default.
• W2012608710 created "2016-06-24" @default.
• W2012608710 creator A5029399586 @default.
• W2012608710 creator A5051019897 @default.
• W2012608710 creator A5056080018 @default.
• W2012608710 creator A5073465100 @default.
• W2012608710 creator A5081027780 @default.
• W2012608710 creator A5085254248 @default.
• W2012608710 date "1997-05-01" @default.
• W2012608710 modified "2023-10-10" @default.
• W2012608710 title "INCLUSION COMPLEXATION OF CYCLOBIS(PARAQUAT-p-PHENYLENE) AND RELATED CYCLOPHANE DERIVATIVES WITH SUBSTITUTED AROMATICS: COOPERATIVE NON-COVALENT CAVITY AND EXTERNAL INTERACTIONS" @default.
• W2012608710 cites W1964112344 @default.
• W2012608710 cites W1964277385 @default.
• W2012608710 cites W1966547974 @default.
• W2012608710 cites W1969328053 @default.
• W2012608710 cites W1969885133 @default.
• W2012608710 cites W1970900112 @default.
• W2012608710 cites W1971074332 @default.
• W2012608710 cites W1973570552 @default.
• W2012608710 cites W1973946055 @default.
• W2012608710 cites W1974375246 @default.
• W2012608710 cites W1976106600 @default.
• W2012608710 cites W1982242658 @default.
• W2012608710 cites W1985572074 @default.
• W2012608710 cites W1991340899 @default.
• W2012608710 cites W1991921654 @default.
• W2012608710 cites W1994001893 @default.
• W2012608710 cites W2006924778 @default.
• W2012608710 cites W2010349118 @default.
• W2012608710 cites W2024021131 @default.
• W2012608710 cites W2027814028 @default.
• W2012608710 cites W2030082437 @default.
• W2012608710 cites W2030153354 @default.
• W2012608710 cites W2031182141 @default.
• W2012608710 cites W2031890789 @default.
• W2012608710 cites W2035466723 @default.
• W2012608710 cites W2036324186 @default.
• W2012608710 cites W2045045577 @default.
• W2012608710 cites W2047839134 @default.
• W2012608710 cites W2048486567 @default.
• W2012608710 cites W2049630963 @default.
• W2012608710 cites W2049669820 @default.
• W2012608710 cites W2058031842 @default.
• W2012608710 cites W2062982547 @default.
• W2012608710 cites W2066780167 @default.
• W2012608710 cites W2069169361 @default.
• W2012608710 cites W2077973224 @default.
• W2012608710 cites W2079604571 @default.
• W2012608710 cites W2082291451 @default.
• W2012608710 cites W2110366203 @default.
• W2012608710 cites W2135183779 @default.
• W2012608710 cites W2145065557 @default.
• W2012608710 cites W2147011143 @default.
• W2012608710 cites W2152259069 @default.
• W2012608710 cites W2152455696 @default.
• W2012608710 cites W2155358697 @default.
• W2012608710 cites W2949710157 @default.
• W2012608710 doi "https://doi.org/10.1002/(sici)1099-1395(199705)10:5<369::aid-poc917>3.0.co;2-i" @default.
• W2012608710 hasPublicationYear "1997" @default.
• W2012608710 type Work @default.
• W2012608710 sameAs 2012608710 @default.
• W2012608710 citedByCount "23" @default.
• W2012608710 countsByYear W20126087102015 @default.
• W2012608710 countsByYear W20126087102016 @default.
• W2012608710 crossrefType "journal-article" @default.
• W2012608710 hasAuthorship W2012608710A5029399586 @default.
• W2012608710 hasAuthorship W2012608710A5051019897 @default.
• W2012608710 hasAuthorship W2012608710A5056080018 @default.
• W2012608710 hasAuthorship W2012608710A5073465100 @default.
• W2012608710 hasAuthorship W2012608710A5081027780 @default.
• W2012608710 hasAuthorship W2012608710A5085254248 @default.
• W2012608710 hasConcept C115624301 @default.
• W2012608710 hasConcept C117626034 @default.
• W2012608710 hasConcept C139287275 @default.
• W2012608710 hasConcept C139358910 @default.
• W2012608710 hasConcept C147597530 @default.
• W2012608710 hasConcept C147789679 @default.
• W2012608710 hasConcept C148093993 @default.
• W2012608710 hasConcept C178790620 @default.
• W2012608710 hasConcept C185592680 @default.
• W2012608710 hasConcept C2778624557 @default.
• W2012608710 hasConcept C2780471494 @default.
• W2012608710 hasConcept C32909587 @default.
• W2012608710 hasConcept C71240020 @default.
• W2012608710 hasConcept C8010536 @default.
• W2012608710 hasConcept C93275456 @default.
• W2012608710 hasConceptScore W2012608710C115624301 @default.
• W2012608710 hasConceptScore W2012608710C117626034 @default.
• W2012608710 hasConceptScore W2012608710C139287275 @default.
• W2012608710 hasConceptScore W2012608710C139358910 @default.
• W2012608710 hasConceptScore W2012608710C147597530 @default.
• W2012608710 hasConceptScore W2012608710C147789679 @default.
• W2012608710 hasConceptScore W2012608710C148093993 @default.
• W2012608710 hasConceptScore W2012608710C178790620 @default.
• W2012608710 hasConceptScore W2012608710C185592680 @default.
• W2012608710 hasConceptScore W2012608710C2778624557 @default.
• W2012608710 hasConceptScore W2012608710C2780471494 @default.
• W2012608710 hasConceptScore W2012608710C32909587 @default.

• next