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See ref. [11] for the complete experimental procedures and NMR characterization of compounds 2-10 and 13-15
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See ref. [11] for the complete experimental procedures and NMR characterization of compounds 2-10 and 13-15.
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note
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13C NMR assignments reported here.
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36
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12444292516
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note
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1H NMR assignments and δ difference maps of ethidium chloride (1), 3,8-diamino-6- phenylphenanthridine (16), 5-ethyl-6-phenylphenanthridinium chloride (11), and 6-phenylphenanthridine (17).
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37
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8 may be dominated by differences in electrone-gativities of nitrogen versus hydrogen and may, therefore, not be indicative of the π-electron densities at these positions.
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46
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12444321148
-
-
note
-
6 bond is, in fact, nearly a full double bond.
-
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-
47
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12444284795
-
-
note
-
[45]
-
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-
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48
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-
12444261490
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note
-
See Supporting Information for IR spectra of ethidium chloride (1), tetramethyl-ethidium chloride (12), and 5-ethyl-6-phenylphenanthridinium chloride (11).
-
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-
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49
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0003608530
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12444290673
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note
-
Early theoretical studies claim that the 6-phenyl ring of ethidium is responsible for its lack of planarity (see ref. [26]). A survey of the Cambridge Crystallographic Database, however, suggests that electron donating groups break the planarity of aromatic systems more effectively than phenyl rings. This can be observed for the following series of phenanthrine-based compounds (twist angles indicated in parenthesis): phenanthrine (0.8), 6-napthyl-phenanthrine (0.9), 6-(N,N-dimethyl aniline)-phenanthrine (2.0).
-
-
-
-
52
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-
12444288293
-
-
note
-
The atomic coordinates of the hydrogen atoms were determined using electron difference maps. See Supporting Information for the ORTEP drawing and crystallographic parameters for compounds 1-3. CCDC-247 564 (1), -247 565 (2), and -247 566 (3) contain the atomic coordinates for these structures. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or deposit@ ccdc.cam.uk).
-
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53
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12444312727
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note
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5.
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54
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12444291915
-
-
note
-
A linear correlation between bond-length/bond-order has already been established for the nitrogen-carbon bonds of phenanthidine-containing molecules (see ref. [42]).
-
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57
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12444284794
-
-
note
-
13C chemical shifts very similar to the nitrogen-bound carbon of aniline. This supports the premise that the contributions made by N-C polarization and hybridization should not have a significant influence on the charges calculated at these positions.
-
-
-
-
60
-
-
12444321717
-
-
note
-
[33]
-
-
-
-
61
-
-
12444301536
-
-
note
-
6. This position is expected to be electropositive (see Supporting Information and refs. [22] and [59]).
-
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65
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0029830638
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69
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12444309112
-
-
note
-
Crystal structures of ethidium intercalated into nucleotide diphosphates (see ref. [12] for an example) are currently the only high-resolution structures of DNA-ethidium intercalation complexes available. These data provide evidence that ethidium can intercalate from both the major and minor grooves of DNA.
-
-
-
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